Polymacromonomer and process for production thereof

ABSTRACT

This invention relates to a polymacromonomer comprising at least one macromonomer and from 0 to 20 wt % of a C 2  to C 12  comonomer, wherein the macromonomer has vinyl termination of at least 70%, and wherein the polymacromonomer has: a) a g value of less than 0.6, b) an Mw of greater than 30,000 g/mol, c) an Mn of greater than 20,000 g/mol, d) a branching index (g′) vis  of less than 0.5, e) less than 25% vinyl terminations, f) at least 70 wt % macromonomer, based upon the weight of the polymacromonomer, g) from 0 to 20 wt % aromatic containing monomer, based upon the weight of the polymacromonomer and h) optionally, a melting point of 50° C. or more. This invention also relates to processes to make such polymacromonomers.

PRIORITY CLAIM

This application is a continuation of U.S. Ser. No. 12/488,066, filedJun. 19, 2009, granted as U.S. Pat. No. 8,283,428, which is acontinuation in part of U.S. Ser. No. 12/143,663 filed Jun. 20, 2008,granted as U.S. Pat. No. 8,372,930, which are incorporated herein.

FIELD OF THE INVENTION

This invention relates to polymacromonomers having lower amounts of C₂to C₁₈ olefin monomers and processes to produce such polymacromonomers.

BACKGROUND OF THE INVENTION

Polyolefins are of great interest in industry as they have many uses inmany different areas. For example, polyolefins, such as polyethylene andpolypropylene, are often used in everything from waxes and plasticizersto films and structural components. Of late many have been interested inmodifying the architecture of such polyolefins in the hopes of obtainingnew and better combinations of properties. One method of controllingpolyolefin architecture is to select monomers that will impart specificcharacteristics or tailoring the monomers used. For example, severalhave tried to produce large “monomers” called “macromonomers” or“macromers” having amounts of vinyl, vinylidene or vinylene terminationthat can be polymerized with smaller olefins such as ethylene orpropylene to impart long chain branching, structural properties, etc. toa polyolefin. Typically, vinyl macromonomers are found more useful oreasier to use than vinylene or vinylidene macromonomers. Examples ofmethods to produce various vinyl terminated macromonomers are disclosedin U.S. Pat. Nos. 6,117,962; and 6,555,635; Small, Brookhart, Bennett, JAm Chem Soc 120, 1998, 4049; and Britovsek, et al. Chem. Comm. 1998,849; Su, et al. Organomet. 25, 2006, 666. See also B. L. Small and M.Brookhart, “Polymerization of Propylene by a New Generation of IronCatalysts: Mechanisms of Chain Initiation, Propagation, and Termination”Macromol. 32 1999, 2322; “Metallocene-Based Branch-Block ThermoplasticElastomers”, E. J. Markel, W. Weng, A. J. Peacock, and A. H. Dekmezian,Macromol. 33 2000, 8541-8548; and A. E. Cheman, E. B. Lobkovski, and G.W. Coates, Macromol 38 2005, 6259-6268.

Others have tried processes that produce a macromonomer then polymerizeit with another smaller olefin, such as ethylene or propylene. Examplesinclude U.S. Pat. No. 6,573,350, US 2004-0138392 A1, US 2004-0127614 A1,U.S. Pat. No. 7,223,822, and Lutz et al, Polymer 47, 2006, 1063-1072.Similar examples of macromonomer re-insertion type polymerizationsinclude U.S. Pat. No. 6,225,432 and T. Shiono, et al. Macromolecules 32,1999, 3723. Typically these polymerizations result in a rather lowamount of the macromonomer being inserted into the growing polymerchain. For example, Shiono et al. report incorporating up to 3.8 mol %of atactic polypropylene macromonomer (Mn 630) in isotacticpolypropylene having Mn of approximately 213,000.

Others have suggested in-situ variations where the macromonomer isproduced in the same reactor that the polymerization occurs in, suchthat the macromonomer is consumed as it is produced. Examples includeU.S. Pat. No. 7,294,681, US 2004-0127614, and U.S. Pat. No. 7,223,822,as well as tandem polymerization catalysts such as discussed by Bazanand coworkers (Chemical Rev 2005, 105, 1001-1020 and referencestherein). In many cases, long chain branched polyolefins can be producedin-situ under conditions that favor macromonomer production and itsconsumption in subsequently growing chains (See Chemical Rev 2005, 105,1001-1020 and references therein).

In other areas, low molecular weight polymers and oligomers of largermonomers (typically referred to as polyalphaolefins), such as octene,decene and dodecene, have been made for uses in lubricants andadditives. For examples please see WO 2007/011459 A1 and U.S. Pat. No.6,706,828. Others have made various polyalphaolefins, such aspolydecene, using various metallocene catalysts not typically known toproduce polymers or oligomers with any specific tacticity. Examplesinclude WO 96/23751, EP 0 613 873, U.S. Pat. Nos. 5,688,887, and6,043,401, US 2003/0055184, U.S. Pat. Nos. 6,548,724, 5,087,788,6,414,090, 6,414,091, 4,704,491, 6,133,209, and 6,713,438. Many of thesepolyalphaolefin molecules have terminal unsaturation that is typicallyhydrogenated or functionalized prior to use as a lubricant or fueladditive.

Others (VanderHart, et al. Macromol. Chem. Phys. 2004, 205, 1877-1885)have made poly(1-octadecene) using titanium tetrachloride supported onmagnesium dichloride activated by triethylaluminum. Specifically,VanderHart et al. homopolymerize C₁₈H₃₆ (Mw=252.3; MWD 1.0) to obtainproduct having a broad composition distribution.

Others have focused on making comb polymers through anionicpolymerization. The comb polymers can be made into model combpolyolefins through hydrogenation. See Hadjichristidis, Lohse et al (seeAnionic homo- and copolymerization of styrenic triple-tailedpolybutadiene macromonomers Nikopoulou A, Iatrou H, Lohse D J,Hadjichristidis N Journal of Polymer Science Part A—Polymer Chemistry 45(16): 3513-3523 Aug. 15, 2007; and “Linear Rheology of Comb Polymerswith Star-like Backbones: Melts and Solutions”, Rheologica Acta, 2006,vol. 46, no. 2, pp. 273-286.)

Likewise, J. F. Lahitte, et al. Homopolymerization of Allyl or UndecenylPolystyrene Macromonomers via Coordination Polymerization CatalystSystem, Polym. Preprint, ACS, Div. Polym. Chem. 2003 44(2) 46-47,disclose polystyryl macromonomers that produce glassy products.

Others (Lahitte, et al. Macromol Rap Comm. 25, 2004, 1010-1014) havemade polymers of vinyl terminated polystyrene-containing macromonomersusing cyclopentadienyl titanium trifluoride in combination withmethylalumoxane in toluene at 50° C. See also Lutz, et al. Polymer, 47,2006, 1063-1072 where macromomers of ω-allyl polystyrene, ω-undecenylpolystyrene or α,ω-undecenyl polystyrene were polymerized with ethyleneusing a coordination catalyst. The macromomers were incorporated intothe olefin chains at levels of about 2.1 to 15.6 wt %.

Additional references of interest include: Chen, et al. JPS, Part BPolym. Phys. 38, 2965-2975 (2000); Schulze, et al. Macromolecules, 2003,36, 4719-4726; Ciolino, et al. Journal of Polymer Science: Part A:Polymer Chemistry, Vol. 42, 2462-2473 (2001); Djalali, et al. Macromol.Rapid. Commun 20, 444-449 (1999); U.S. Pat. No. 6,197,910; WO 93/21242;and WO 93/12151.

SUMMARY OF THE INVENTION

This invention relates to a polymacromonomer comprising (alternatelyconsisting essentially of, alternately consisting of) at least onemacromonomer and from 0 to 20 wt % of a C₂ to C₁₈ comonomer, wherein thehydrocarbon macromonomer has:

1) from 20 to 600 carbon atoms, (as determined from GPC-DRI Mn)

2) an Mn of 280 g/mol or more (as determined by ¹H NMR),

3) an Mw of 400 g/mol or more (as determined by GPC),

4) an Mz of 600 g/mol or more (as determined by GPC),

5) an Mw/Mn of 1.5 or more, (Mw determined by GPC, Mn determined by ¹HNMR)

6) at least 70% vinyl termination (relative to total unsaturation) (asdetermined by ¹H NMR),

7) a melting point of 60° C. or more (DSC, second melt), and

8) less than 5 wt % aromatic containing monomer (based upon the weightof the macromonomer) as determined by ¹H NMR; and

wherein the polymacromonomer has:

a) a g value of less than 0.6 (as determined by GPC),

b) an Mw of greater than 20,000 g/mol (as determined by GPC),

c) an Mn of greater than 10,000 g/mol (as determined by ¹H NMR),

d) a branching index (g′)_(vis) of less than 0.5 (as determined by GPC),

e) a melting point of 50° C. or more (DSC second melt),

f) less than 20% vinyl termination (relative to total unsaturation) (asdetermined by ¹HNMR),

g) and where the polymacromonomer comprises at least 70 wt %macromonomer, based upon the weight of the polymacromonomer, and

h) less than 5 wt % aromatic containing monomer (based upon the weightof the polymacromonomer) as determined by ¹H NMR.

In another embodiment, this invention relates to a polymacromonomercomprising (alternately consisting essentially of, alternatelyconsisting of) at least one macromonomer and from 0 to 20 wt % of a C₂to C₁₈ comonomer, wherein the polymacromonomer has:

a) a g value of less than 0.6,

b) an Mw of greater than 20,000 g/mol,

c) an Mn of greater than 10,000 g/mol,

d) a branching index (g′)_(vis) of less than 0.5,

e) optionally, a melting point of 0° C. or more,

f) less than 20% vinyl termination (relative to total unsaturation),

g) and where the polymacromonomer comprises at least 70 wt %macromonomer, based upon the weight of the polymacromonomer, and

h) less than 5 wt % aromatic containing monomer (based upon the weightof the polymacromonomer) wherein the macromonomer comprises one or moreof:

i) propylene co-oligomer having an Mn of 300 to 30,000 g/mol (asmeasured by ¹H NMR) comprising 10 to 90 mol % propylene and 10 to 90 mol% of ethylene, wherein the oligomer has at least X % allyl chain ends(relative to total unsaturations), where: 1) X=(−0.94 (mol % ethyleneincorporated)+100), when 10 to 60 mol % ethylene is present in theco-oligomer, and 2) X=45, when greater than 60 and less than 70 mol %ethylene is present in the co-oligomer, and 3) X=(1.83*(mol % ethyleneincorporated)−83), when 70 to 90 mol % ethylene is present in theco-oligomer; and/or

ii) propylene oligomer, comprising more than 90 mol % propylene and lessthan 10 mol % ethylene, wherein the oligomer has: at least 93% allylchain ends, an Mn of about 500 to about 20,000 g/mol (as measured by ¹HNMR), an isobutyl chain end to allylic vinyl group ratio of 0.8:1 to1.35:1.0, and less than 1400 ppm aluminum; and/or

iii) propylene oligomer, comprising at least 50 mol % propylene and from10 to 50 mol % ethylene, wherein the oligomer has: at least 90% allylchain ends, Mn of about 150 (preferably 250) to about 10,000 g/mol (asmeasured by ¹H NMR), and an isobutyl chain end to allylic vinyl groupratio of 0.8:1 to 1.3:1.0, wherein monomers having four or more carbonatoms are present at from 0 to 3 mol %; and/or

iv) propylene oligomer, comprising at least 50 mol % propylene, from 0.1to 45 mol % ethylene, and from 0.1 to 5 mol % C4 to C12 olefin, whereinthe oligomer has: at least 87% allyl chain ends (alternately at least90%), an Mn of about 150 (preferably 250) to about 10,000 g/mol, (asmeasured by ¹H NMR), and an isobutyl chain end to allylic vinyl groupratio of 0.8:1 to 1.35:1.0; and/or

v) propylene oligomer, comprising at least 50 mol % propylene, from 0.1to 45 wt % ethylene, and from 0.1 to 5 mol % diene, wherein the oligomerhas: at least 90% allyl chain ends, an Mn of about 150 to about 10,000g/mol (as measured by ¹H NMR), and an isobutyl chain end to allylicvinyl group ratio of 0.7:1 to 1.35:1.0; and/or

vi) a homooligomer, comprising propylene, wherein the oligomer has: atleast 93% allyl chain ends, an Mn of about 500 to about 20,000 g/mol (asmeasured by ¹H NMR), an isobutyl chain end to allylic vinyl group ratioof 0.8:1 to 1.2:1.0, and less than 1400 ppm aluminum.

This invention further relates to a homogeneous process to make sucholigomers i) to vi) and thereafter produce polymacromonomers, bycontacting the oligomer and up to 40 wt % C₂ to C₁₂ comonomer in thefeedstream entering the reactor (preferably from 0 to 30 wt %,preferably from 0 to 20 wt %, preferably from 0 to 10 wt %, preferablyfrom 0 to 5 wt %, preferably from 0 to 1 wt % of C₂ to C₁₂ comonomer),with a catalyst system capable of polymerizing vinyl terminatedmacromonomer (preferably comprising activator and a compound representedby the formula I, II, III, or IV below). For more detailed informationon oligomers i) to vi) and processes to make them, please see U.S. Ser.No. 12/143,663, filed Jun. 20, 2008, incorporated by reference herein.

This invention relates to a polymacromonomer comprising (alternatelyconsisting essentially of, alternately consisting of) at least onemacromonomer and from 0 to 20 wt % of a C₂ to C₁₈ comonomer, wherein thehydrocarbon macromonomer has:

1) from 20 to 600 carbon atoms, (as determined by GPC-DRI Mn)

2) an Mn of 280 g/mol or more (as determined by ¹H NMR),

3) an Mw of 400 g/mol or more (as determined by GPC),

4) an Mz of 600 g/mol or more (as determined by GPC),

5) an Mw/Mn of 1.5 or more, (Mw determined by GPC, Mn determined by ¹HNMR)

6) at least 70% vinyl termination (relative to total unsaturation) (asdetermined by ¹HNMR),

7) a heat of melting (Hm) of 20 J/g or less (preferably 15 J/g or less),and

8) less than 5 wt % aromatic containing monomer (based upon the weightof the macromonomer) as determined by ¹H NMR; and

wherein the polymacromonomer has:

a) a g value of less than 0.6 (as determined by GPC),

b) an Mw of greater than 20,000 g/mol (as determined by GPC),

c) an Mn of greater than 10,000 g/mol (as determined by ¹HNMR),

d) a branching index (g′)_(vis) of less than 0.5 (as determined by GPC),

e) an Hm of 20 J/g or less, preferably 15 J/g or less,

f) less than 20% vinyl termination (relative to total unsaturation) (asdetermined by ¹HNMR),

g) and where the polymacromonomer comprises at least 70 wt %macromonomer, based upon the weight of the polymacromonomer, and

h) less than 5 wt % aromatic containing monomer (based upon the weightof the polymacromonomer).

This invention also relates to a process to produce polymacromonomercomprising contacting macromonomer and up to 40 wt % C₂ to C₁₈ comonomerin the feedstream entering the reactor (preferably from 0 to 30 wt %,preferably from 0 to 20 wt %, preferably from 0 to 10 wt %, preferablyfrom 0 to 5 wt %, preferably from 0 to 1 wt % of C₂ to C₁₈ comonomer),with a catalyst system capable of polymerizing vinyl terminatedmacromonomer, under polymerization conditions of a temperature of 60 to130° C. and a reaction time of 1 to 90 minutes, wherein the weight ratioof all comonomer present in the reactor to all macromonomer present inthe reactor is 2:1 or less and where conversion of macromonomer topolymacromonomer is 70 wt % or more (as determined by infraredspectroscopy (IR) on samples taken at the entrance and exit of thereactor, specifically one should perform an IR of the macromonomer as itenters reactor and find resonance peak of the vinyl group, then measurethe same peak on samples taken at the reactor exit and the volume shouldbe 70% consumed).

This invention further relates to a process, preferably an in-lineprocess, preferably a continuous process, to produce polymacromonomer,comprising introducing monomer and catalyst system into a reactor,obtaining a reactor effluent containing macromonomer, removing (such asflashing off) solvent, unused monomer and other volatiles, obtainingmacromonomer, introducing macromonomer and catalyst system into areaction zone (such as a reactor (such as a batch, CSTR or tubularreactor), an extruder, a pipe and/or a pump) and obtainingpolymacromonomer. Reaction zone and reactor may be used synonymouslyherein.

This invention also relates to a two stage process to obtainpolymacromonomer comprising contacting olefin monomer with a catalystsystem, obtaining macromonomer and thereafter contacting themacromonomer with a catalyst system and thereafter obtainingpolymacromonomer.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a chart of the range of chemical shift assignments for thepolymacromonomer prepared in Example 1.

FIG. 2 is an illustration of ¹³C NMR nomenclature of the resonancesspecific to homopolyethylene macromonomers inserted to make thepolymacromonomer (e.g no comonomer).

FIG. 3 is an illustration of a naming convention described herein.

FIG. 4 is a graph of Rg versus MW for Example 2 as determined byGPC-MALLS.

FIG. 5 is an overlay of the ¹HNMR spectra for PE_(mac-1) (bottom)showing the vinyl groups and the ¹HNMR spectra for Example 1 showing thelack of vinyl groups.

DEFINITIONS

A catalyst system is defined to comprise a catalyst compound plus anactivator.

For the purposes of this invention and the claims thereto when a polymeris referred to as comprising an olefin, the olefin present in thepolymer is the polymerized form of the olefin. Likewise when catalystcomponents are described as comprising neutral stable forms of thecomponents, it is well understood by one of ordinary skill in the art,that the ionic form of the component is the form that reacts with themonomers to produce polymers. In addition, a reactor is any container(s)in which a chemical reaction occurs.

As used herein, the new numbering scheme for the Periodic Table Groupsis used as published in CHEMICAL AND ENGINEERING NEWS, 63(5), 27 (1985).

For purposes of this invention, the term “oligomer” is defined to havean Mn of from 100 to 1200 g/mol as measured by ¹H NMR. The term“polymer” is defined to have an Mn of more than 1200 g/mol as measuredby ¹H NMR. When an oligomer is referred to as comprising an olefin, theolefin present in the oligomer is the oligomerized form of the olefin. Aco-oligomer is an oligomer comprising at least two different monomerunits (such as propylene and ethylene). A homo-oligomer is an oligomercomprising units of the same monomer (such as propylene). A propyleneoligomer/polymer/macromonomer/polymacromonomer is anoligomer/polymer/macromonomer/polymacromonomer having at least 50 mol %of propylene, respectively. As used herein, Mn is number averagemolecular weight (measured by ¹H NMR according to the proceduredescribed in the Experimental section below), Mw is weight averagemolecular weight (measured by Gel Permeation Chromatography according tothe procedure described in the Experimental section below), and Mz is zaverage molecular weight (measured by Gel Permeation Chromatographyaccording to the procedure described in the Experimental section below),wt % is weight percent, and mol % is mole percent. Molecular weightdistribution (MWD) is defined to be Mw divided by Mn. Unless otherwisenoted, all molecular weight units (e.g., Mw, Mn, Mz) are g/mol.

The term “vinyl termination”, also referred to as allyl chain end(s)” or“vinyl content” is defined to be an oligomer or polymer having at leastone terminus represented by formula I:

where the “●●●●” represents the oligomer or polymer chain. In apreferred embodiment the allyl chain end is represented by the formulaII:

The amount of allyl chain ends (also called % vinyl termination) isdetermined using ¹H NMR at 120° C. using deuterated tetrachloroethane asthe solvent on a 500 MHz machine and in selected cases confirmed by ¹³CNMR. Resconi has reported proton and carbon assignments (neatperdeuterated tetrachloroethane used for proton spectra while a 50:50mixture of normal and perdeuterated tetrachloroethane was used forcarbon spectra; all spectra were recorded at 100° C. on a Bruker AM 300spectrometer operating at 300 MHz for proton and 75.43 MHz for carbon)for vinyl terminated propylene oligomers in J American Chemical Soc 1141992, 1025-1032 that are useful herein.

“Isobutyl chain end” is defined to be an oligomer having at least oneterminus represented by the formula:

where M represents the oligomer chain. In a preferred embodiment, theisobutyl chain end is represented by one of the following formulae:

where M represents the oligomer chain.

The percentage of isobutyl end groups is determined using ¹³C NMR (asdescribed in the example section) and the chemical shift assignments inResconi et al, J. Am. Chem. Soc. 1992, 114, 1025-1032 for 100% propyleneoligomers and set forth in FIG. 2 for E-P oligomers.

The “isobutyl chain end to allylic vinyl group ratio” is defined to bethe ratio of the percentage of isobutyl chain ends to the percentage ofallylic vinyl groups.

An “aromatic containing monomer” is a C₄ to C₃₆ hydrocarbyl groupcontaining at least one aromatic group. Examples include styrene,alpha-methyl styrene, para-methyl-styrene, and4-(dichloromethylsilyl)diphenylethylene. An aromatic group is defined tobe a cyclic group having at least one pair of conjugated double bonds.Examples include cyclopentadiene, indene, fluorene, and benzene.

A “styrenic” monomer is a monomer comprising a styrene unit, such as:

wherein each R is, individually, hydrogen or a C₁ to C₁₂ hydrocarbylgroup, or C₁ to C₁₂ substituted hydrocarbyl group, preferablysubstituted with a halogen (such as Br or Cl).

A reaction zone is any vessel where a reaction occurs, such as glassvial, a polymerization reactor, reactive extruder, tubular reactor andthe like.

As used herein the term continuous means a system that operates withoutinterruption or cessation. For example a continuous process to produce apolymer would be one where the reactants are continually introduced intoone or more reactors and polymer product is continually withdrawn.

DETAILED DESCRIPTION

In another embodiment, this invention relates to a polymacromonomercomprising at least one macromonomer and from 0.1 to 20 wt % (preferably0.5 to 15 wt %, preferably 1 to 10 wt %, preferably 1 to 5 wt %,preferably from 0 to 5 mol %) of a C2 to C18 comonomer (preferably a C₂to C₁₂ comonomer, preferably ethylene, propylene, butene, hexene,4-methyl pentene-1, and 3-methyl pentene-1 and/or norbornene) whereinthe macromonomer has:

1) from 20 to 800 carbon atoms (preferably from 20 to 700, preferablyfrom 20 to 600, preferably from 20 to 500, preferably from 20 to 400,preferably from 20 to 300, preferably from 20 to 200, preferably from 30to 175),

2) an Mn of 280 g/mol or more, (preferably from 280 to 15,000,preferably from 280 to 10,000, preferably from 280 to 12,000, preferablyfrom 280 to 8,000, preferably 280 to 6,000, preferably 300 to 5,000,preferably 350 to 3,000, preferably 350 to 2,000),

3) an Mw of 400 g/mol or more (preferably from 400 to 50,000, preferablyfrom 400 to 20,000, preferably from 450 to 15,000, preferably 450 to10,000, preferably 450 to 5,000, preferably 450 to 3,000),

4) an Mz of 600 g/mol or more, (preferably from 600 to 35,000,preferably from 600 to 30,000, preferably from 600 to 25,000, preferablyfrom 600 to 20,000, preferably from 600 to 15,000, preferably 600 to10,000, preferably 600 to 5,000, preferably 750 to 3,000),

5) an Mw/Mn of 1.5 or more, (preferably 1.5 to 7, preferably from 1.5 to6, preferably from 1.6 to 5, preferably from 1.8 to 4, preferably from1.5 to 3, preferably from 1.5 to 2.5),

6) vinyl termination (also referred to as vinyl content) of 70% or more,relative to total unsaturations, (as measured by ¹H NMR) (preferably 75%or more, preferably 80% or more, preferably 85% or more, preferably 90%or more, preferably 95% or more, preferably 98% or more), and

7) a melting point Tm of 60° C. or more (preferably 70° C. or more,preferably 80° C. or more, preferably 90° C. or more, preferably 100° C.or more, preferably 110° C. or more, preferably 120° C. or more,preferably 130° C. or more) or alternately an Hm of 20 J/g or less,preferably 15 J/g or less,

8) from 0 to 10 wt % aromatic containing monomer, such as styrenicmonomer, (preferably 0 to 5 wt %, preferably 0 to 1 wt %, alternately 0wt %), based upon the weight of the macromonomer; and wherein thepolymacromonomer has:

a) a g value of less than 0.6 (preferably less than 0.5, preferably lessthan 0.4, preferably less than 0.3, alternately less than 0.2),

b) an Mw of greater than 30,000 g/mol (preferably 40,000 to 3,000,000,preferably 60,000 to 1,500,000),

c) an Mn of greater than 20,000 g/mol (preferably 40,000 to 2,000,000,preferably 60,000 to 1,000,000),

d) a branching index (g′)_(vis) of less than 0.5 (preferably less than0.4, preferably less than 0.3, preferably less than 0.2),

e) a melting point of 50° C. or more (preferably 60° C. or more,preferably 70° C. or more, preferably 80° C. or more, preferably 90° C.or more, preferably 100° C. or more, preferably 120° C. or more), oralternately an Hm of 20 J/g or less, preferably 15 J/g or less, and

f) from 0 to 10 wt % aromatic containing monomer, such as styrenicmonomer, (preferably 0 to 5 wt %, preferably 0 to 1 wt %, alternately 0wt %), based upon the weight of the polymacromonomer.

In a preferred embodiment the macromonomer is not aromatic (comprisesless than 5 wt % aromatic containing monomers, preferably less than 1 wt%, preferably 0 wt %), preferably is not styrenic (comprises less than 5wt % styrenic monomers, preferably less than 1 wt %, preferably 0 wt %).

In a preferred embodiment, the macromonomer used herein has:

1) from 20 to 800 carbon atoms (preferably from 20 to 700, preferablyfrom 20 to 600, preferably from 20 to 500, preferably from 20 to 400,preferably from 20 to 300, preferably from 20 to 200, preferably from 30to 175),

2) an Mn of 280 g/mol or more, (preferably from 280 to 15,000,preferably from 280 to 10,000, preferably from 280 to 12,000, preferablyfrom 280 to 8,000, preferably 280 to 6,000, preferably 300 to 5,000,preferably 350 to 3,000, preferably 350 to 2,000),

3) an Mw of 400 g/mol or more (preferably from 400 to 50,000, preferablyfrom 400 to 20,000, preferably from 450 to 15,000, preferably 450 to10,000, preferably 450 to 5,000, preferably 450 to 3,000),

4) an Mz of 600 g/mol or more, (preferably from 600 to 35,000,preferably from 600 to 30,000, preferably from 600 to 25,000, preferablyfrom 600 to 20,000, preferably from 600 to 15,000, preferably 600 to10,000, preferably 600 to 5,000, preferably 750 to 3,000),

5) an Mw/Mn of 1.5 or more, (preferably 1.5 to 7, preferably from 1.5 to6, preferably from 1.6 to 5, preferably from 1.8 to 4, preferably from1.5 to 3, preferably from 1.5 to 2.5),

6) a vinyl content of 70% or more, relative to total unsaturations,(preferably 70% or more, preferably 80% or more, preferably 85% or more,preferably 90% or more, preferably 95% or more, preferably 97%,preferably 98% or more, preferably 99% or more)

7) a melting point (DSC, second melt) of 60° C. or more (preferably 70°C. or more, preferably 80° C. or more, preferably 90° C. or more,preferably 100° C. or more, preferably 110° C. or more, preferably 120°C. or more, preferably 130° C. or more) or alternately an Hm of 20 J/gor less, preferably 15 J/g or less; and

8) from 0 to 10 wt % of aromatic containing monomer, such as styrenicmonomer (preferably 0 to 5 wt %, preferably 0 to 1 wt %, alternately 0wt %) based upon the weight of the macromonomer. (Aromatic content in apolymer is determined by ¹HNMR).

Mw, Mz, and Number of carbon atoms are determined by GPC according tothe procedure described in the Experimental section below. Mn isdetermined by ¹HNMR according to the procedure described in theExperimental section below. Branching index (g′)_(vis) is determinedaccording to the procedure described in the Experimental section below.Vinyl content (%) is determined as described above and in theExperimental section below. Melting point is determined by differentialscanning calorimetry as described in the Experimental section below. “gvalue” is determined by the GPC procedure described in the Experimentalsection below and according to the methods in Macromolecules, 2001, 34,6812-6820.

In another embodiment, the macromonomer used herein is a propylenehomo-oligomer, comprising propylene and less than 0.5 wt % comonomer,preferably 0 wt % comonomer, wherein the oligomer has:

-   -   i) at least 93% allyl chain ends (preferably at least 95%,        preferably at least 97%, preferably at least 98%);    -   ii) a number average molecular weight (Mn) of about 500 to about        20,000 g/mol, as measured by ¹H NMR (preferably 500 to 15,000,        preferably 600 to 10,000, preferably 800 to 8,000 g/mol,        preferably 900 to 7,000, preferably 1000 to 6,000, preferably        1000 to 5,000);    -   iii) an isobutyl chain end to allylic vinyl group ratio of 0.8:1        to 1.3:1.0;    -   iv) less than 1400 ppm aluminum, (preferably less than 1200 ppm,        preferably less than 1000 ppm, preferably less than 500 ppm,        preferably less than 100 ppm).

In another embodiment, the macromonomer used herein is a propyleneco-oligomer having an Mn of 300 to 30,000 g/mol as measured by ¹H NMR(preferably 400 to 20,000, preferably 500 to 15,000, preferably 600 to12,000, preferably 800 to 10,000, preferably 900 to 8,000, preferably900 to 7,000 g/mol), comprising 10 to 90 mol % propylene (preferably 15to 85 mol %, preferably 20 to 80 mol %, preferably 30 to 75 mol %,preferably 50 to 90 mol %) and 10 to 90 mol % (preferably 85 to 15 mol%, preferably 20 to 80 mol %, preferably 25 to 70 mol %, preferably 10to 50 mol %) of one or more alpha-olefin comonomers (preferablyethylene, butene, hexene, or octene, preferably ethylene), wherein theoligomer has at least X % allyl chain ends (relative to totalunsaturations), where: 1) X=(−0.94 (mol % ethylene incorporated)+100{alternately 1.20 (−0.94 (mol % ethylene incorporated)+100), alternately1.50(−0.94 (mol % ethylene incorporated)+100)}), when 10 to 60 mol %ethylene is present in the co-oligomer, and 2) X=45 (alternately 50,alternately 60), when greater than 60 and less than 70 mol % ethylene ispresent in the co-oligomer, and 3) X=(1.83*(mol % ethyleneincorporated)=83, {alternately 1.20 [1.83*(mol % ethyleneincorporated)=83], alternately 1.50 [1.83*(mol % ethyleneincorporated)−83]}), when 70 to 90 mol % ethylene is present in theco-oligomer. Alternately X is 80% or more, preferably 85% or more,preferably 90% or more, preferably 95% or more.

In an alternate embodiment any of oligomers i) to vi) have at least 80%isobutyl chain ends (based upon the sum of isobutyl and n-propylsaturated chain ends), preferably at least 85% isobutyl chain ends,preferably at least 90% isobutyl chain ends. Alternately, any ofoligomers i) to vi) have an isobutyl chain end to allylic vinyl groupratio of 0.8:1 to 1.35:1.0, preferably 0.9:1 to 1.20:1.0, preferably0.9:1.0 to 1.1:1.0.

In another embodiment, the macromonomer used herein is a propyleneoligomer, comprising more than 90 mol % propylene (preferably 95 to 99mol %, preferably 98 to 9 mol %) and less than 10 mol % ethylene(preferably 1 to 4 mol %, preferably 1 to 2 mol %), wherein the oligomerhas:

at least 93% allyl chain ends (preferably at least 95%, preferably atleast 97%, preferably at least 98%)_(;)

a number average molecular weight (Mn) of about 400 to about 30,000g/mol, as measured by ¹H NMR (preferably 500 to 20,000, preferably 600to 15,000, preferably 700 to 10,000 g/mol, preferably 800 to 9,000,preferably 900 to 8,000, preferably 1000 to 6,000);

an isobutyl chain end to allylic vinyl group ratio of 0.8:1 to 1.35:1.0;and less than 1400 ppm aluminum, (preferably less than 1200 ppm,preferably less than 1000 ppm, preferably less than 500 ppm, preferablyless than 100 ppm).

In another embodiment, the macromonomer used herein is a propyleneoligomer, comprising:

at least 50 (preferably 60 to 90, preferably 70 to 90) mol % propyleneand from 10 to 50 (preferably 10 to 40, preferably 10 to 30) mol %ethylene, wherein the oligomer has:

at least 90% allyl chain ends (preferably at least 91%, preferably atleast 93%, preferably at least 95%, preferably at least 98%);

an Mn of about 150 to about 20,000 g/mol, as measured by ¹H NMR(preferably 200 to 15,000, preferably 250 to 15,000, preferably 300 to10,000, preferably 400 to 9,500, preferably 500 to 9,000, preferably 750to 9,000); and

an isobutyl chain end to allylic vinyl group ratio of 0.8:1 to 1.3:1.0,wherein monomers having four or more carbon atoms are present at from 0to 3 mol % (preferably at less than 1 mol %, preferably less than 0.5mol %, preferably at 0 mol %).

In another embodiment, the macromonomer used herein is a propyleneoligomer, comprising:

at least 50 (preferably at least 60, preferably 70 to 99.5, preferably80 to 99, preferably 90 to 98.5) mol % propylene, from 0.1 to 45(preferably at least 35, preferably 0.5 to 30, preferably 1 to 20,preferably 1.5 to 10) mol % ethylene, and from 0.1 to 5 (preferably 0.5to 3, preferably 0.5 to 1) mol % C₄ to C₁₂ olefin (such as butene,hexene or octene, preferably butene), wherein the oligomer has:

at least 90% allyl chain ends (preferably at least 91%, preferably atleast 93%, preferably at least 95%, preferably at least 98%);

a number average molecular weight (Mn) of about 150 to about 15,000g/mol, as measured by ¹H NMR (preferably 200 to 12,000, preferably 250to 10,000, preferably 300 to 10,000, preferably 400 to 9500, preferably500 to 9,000, preferably 750 to 9,000); and

an isobutyl chain end to allylic vinyl group ratio of 0.8:1 to 1.35:1.0.

In another embodiment, the macromonomer used herein is a propyleneoligomer, comprising:

at least 50 (preferably at least 60, preferably 70 to 99.5, preferably80 to 99, preferably 90 to 98.5) mol % propylene, from 0.1 to 45(preferably at least 35, preferably 0.5 to 30, preferably 1 to 20,preferably 1.5 to 10) mol % ethylene, and from 0.1 to 5 (preferably 0.5to 3, preferably 0.5 to 1) mol % diene (such as C4 to C12 alpha-omegadienes (such as butadiene, hexadiene, octadiene), norbornene, ethylidenenorbornene, vinylnorbornene, norbornadiene, and dicyclopentadiene),wherein the oligomer has:

at least 90% allyl chain ends (preferably at least 91%, preferably atleast 93%, preferably at least 95%, preferably at least 98%);

a number average molecular weight (Mn) of about 150 to about 20,000g/mol, as measured by ¹H NMR (preferably 200 to 15,000, preferably 250to 12,000, preferably 300 to 10,000, preferably 400 to 9,500, preferably500 to 9,000, preferably 750 to 9,000); and

an isobutyl chain end to allylic vinyl group ratio of 0.7:1 to 1.35:1.0.

Any of the macromonomers (preferably the oligomers i) to vi)) preparedherein preferably have less than 1400 ppm aluminum, preferably less than1000 ppm aluminum, preferably less than 500 ppm aluminum, preferablyless than 100 ppm aluminum, preferably less than 50 ppm aluminum,preferably less than 20 ppm aluminum, preferably less than 5 ppmaluminum.

In another preferred embodiment, the macromonomer is amorphous,isotactic or syndiotactic, preferably isotactic. In another embodiment,the macromonomer is a propylene homopolymer or propylene homo-oligomerthat may be amorphous, isotactic or syndiotactic, preferably isotactic.In another embodiment, the macromonomer is a propylene copolymer orpropylene co-oligimer that may be amorphous, isotactic or syndiotactic,preferably isotactic. Amorphous is defined to mean a heat of fusion ofless than 10 J/g. Isotactic is defined to be at least 50% isotacticpentads (as determined by ¹³CNMR as described below) preferably at least60%, preferably at least 70%, preferably at least 80% isotactic pentads.Syndiotactic is defined to be at least 50% syndiotactic pentads (asdetermined by ¹³CNMR as described below) preferably at least 60%,preferably at least 70%, preferably at least 80% syndiotactic pentads.

In any of the embodiments described herein the macromonomer containsonly, or consists essentially of or consists of, C₂ to C₁₈ linear alphaolefin monomer units (preferably C₂ to C₁₂, preferably ethylene,propylene, butene, octene, decene, or dodecene, preferably ethylene andpropylene). In another embodiment the macromonomer does not comprise anystyrene based monomer units. In another embodiment the macromonomer doesnot comprise any cyclic monomer units. In another embodiment themacromonomer does not comprise any aromatic monomer units. In anotherembodiment the macromonomer comprises 1 wt % or less of a styreneicmonomer unit, a cyclic monomer unit or an aromatic monomer unit,preferably less than 0.5 wt %, preferably 0 wt %, based upon the weightof the macromonomer.

In another embodiment the macromonomer comprises less than 30 wt %amorphous material, preferably less than 20 wt %, preferably less than10 wt %, preferably less than 5 wt % amorphous material, based upon theweight of the macromonomer. Percent amorphous material is determined bysubtracting the percent crystallinity from 100. The percentcrystallinity (X %) is calculated using the formula: [area under the DSCcurve (in J/g)/H° (in J/g)]*100, where H° is the heat of fusion for thehomopolymer of the major monomer component. These values for H° are tobe obtained from the Polymer Handbook, Fourth Edition, published by JohnWiley and Sons, New York 1999, except that a value of 290 J/g is used asthe equilibrium heat of fusion (H°) for 100% crystalline polyethylene, avalue of 140 J/g is used as the equilibrium heat of fusion (H°) for 100%crystalline polybutene, and a value of 207 J/g (H°) is used as the heatof fusion for a 100% crystalline polypropylene. The DSC curve isobtained as described in the Experimental section below.

In another embodiment, the macromonomer (particularly oligomers i) toiv)) has a glass transition temperature (Tg) of 0° C. or less (asdetermined by differential scanning calorimetry as described below),preferably −10° C. or less, more preferably −20° C. or less, morepreferably −30° C. or less, more preferably −50° C. or less.

In another embodiment, the macromonomer (particularly oligomers i) toiv)) has a melting point (DSC first melt) of from 60 to 130° C.,alternately 50 to 100° C. In another embodiment, the oligomers describedherein have no detectable melting point by DSC following storage atambient temperature (23° C.) for at least 48 hours.

In another embodiment, the macromonomer (particularly oligomers i) toiv)) is a liquid at 25° C.

In another embodiment, any macromonomer described herein may have a heatof fusion of 50 J/g or more, preferably 75 J/g or more, preferably 100J/g or more, as determined by differential scanning calorimetry asdescribed in the Experimental section below.

In another embodiment, any macromonomer described herein may have apercent crystallinity of 50% or more, preferably 60% or more, preferably70% or more, as determined by DSC as described in the Experimentalsection below.

In another embodiment, any macromonomer described herein contains lessthan 1000 ppm of a group 4 metal (preferably less than 750 ppm or Ti, Hfand/or Zr). Alternately, the macromonomer contains less than 1000 ppm oflithium (preferably less than 750 ppm of lithium).

In a preferred embodiment, any macromonomer described herein comprisesless than 3 wt % of functional groups selected from hydroxide, aryls andsubstituted aryls, halogens, alkoxys, carboxylates, esters, acrylates,oxygen, nitrogen, and carboxyl, preferably less than 2 wt %, morepreferably less than 1 wt %, more preferably less than 0.5 wt %, morepreferably less than 0.1 wt %, more preferably 0 wt %, based upon theweight of the macromonomer.

In another embodiment, the macromer described herein is a propyleneoligomer or polymer. In some embodiments the propylene oligomer orpolymer has one or more of the following properties:

a) a g′_(vis) of 0.95 or less, preferably 0.90 or less, preferably 0.85or less, preferably 0.80 or less, preferably 0.75 or less, preferably0.70 or less); and or

b) an Mw of 5,000 to 100,000 g/mol (preferably 15,000 to 100,000,preferably 20,000 to 75,000 g/mol); and/or

c) a melting point of 90° C. or more (alternately 100° C. or more,alternately 140° C. or more). In a preferred embodiment the propyleneoligomer or polymer is isotactic. Such propylene oligomers or polymersare know in the art and can be made using metallocene catalsyts such asdimethylsilyl-bis(2-methyl,4-phenyl-indenyl)hafniumdimethyl or thecatalyst compounds described in U.S. Pat. No. 7,279,536, typically usedin combination with N,N-dimethylanilinium tetra (perfluorophenyl)borateor N,N-dimethylanilinium tetrakis (heptafluoronaphthyl)borate.

In a preferred embodiment, the macromonomer is a copolymer of ethyleneand propylene, preferably having a Hm of 20 J/g or less (preferably 15J/g or less) comprising from 65 to 80 wt % ethylene and from 20 to 35 wt% propylene, preferably having an Mw of from 5,000 to 100,000 g/mol,preferably 20,000 to 80,000 g/mol. Such copolymers are know in the artand can be made using metallocene catalsyts such as(pentamethylcyclopentadienyl)(1,3-dimethylindenyl)hafnium dimethyl,typically used in combination with N,N-dimethylanilinium tetra(perfluorophenyl)borate or N,N-dimethylanilinium tetrakis(heptafluoronaphthyl)borate.

Macromonomers useful herein may be made by process known in the art toproduce vinyl terminated macromonomers, including those described inU.S. Pat. No. 6,117,962, U.S. Pat. No. 6,555,635, Small, Brookhart,Bennett, JACS120, 1998, 4049, Britovsek, et al. Chem. Comm. 1998, 849.,Su, et al. Organomet. 25, 2006, 666.

In a preferred embodiment, the macromonomers can be produced using oneor more activators in combination with one or more of the catalystcompounds described in: 1) G. J. P. Britovsek, V. C. Gibson, S. J.McTavish, G. A. Solan, B. S. Kimberley, P. J. Maddox, A. J. P. White,Williams, Chem. Comm. 1998, 849; 2) Journal of Organometallic Chemistry,648, 2002, 55; 3) Iron Complexes Bearing 2-Imino-1,10-phenanthrolinylLigands as Highly Active Catalysts for Ethylene Oligomerization,Organometallics, 2006, 666-677; and 4) “Novel Olefin PolymerizationCatalysts Based on Iron and Cobalt”, Chem. Commun 1998, 849.

Particularly useful catalyst compounds to make vinyl terminated ethylenemacromonomers (preferably crystalline, e.g. having at least 40%crystallinity) include those represented by the formula:

Particularly useful catalyst compounds to make vinyl terminatedisotactic propylene macromonomers (preferably crystalline, e.g. havingat least 40% crystallinity) include those represented by the formula:

where M¹ is selected from titanium, zirconium, hafnium, vanadium,niobium, tantalum, chromium, molybdenum, or tungsten (preferablyzirconium and or hafnium);

R¹ and R² are identical or different and are selected from hydrogenatoms, C1-C₁₀ alkyl groups, C1-C10 alkoxy groups, C6-C10 aryl groups,C6-C10 aryloxy groups, C2-C10 alkenyl groups, C2-C40 alkenyl groups,C7-C40 arylalkyl groups, C7-C40 alkylaryl groups, C8-C40 arylalkenylgroups, OH groups or halogen atoms; or conjugated dienes that areoptionally substituted with one or more hydrocarbyl,tri(hydrocarbyl)silyl groups or hydrocarbyltri(hydrocarbyl)silylhydrocarbyl groups (preferably R¹ and R² are analkyl such as methyl or ethyl or are a halide such as chloride);

R₃-R₁₂ are the same or different and are selected from hydrogen atoms,halogen atoms, C1-C10 halogenated or unhalogenated alkyl groups, C6-C10halogenated or unhalogenated aryl groups, C2-C10 halogenated orunhalogenated alkenyl groups, C7-C40 halogenated or unhalogenatedarylalkyl groups, C7-C40 halogenated or unhalogenated alkylaryl groups,C8-C40 halogenated or unhalogenated arylalkenyl groups, —NR′2, —SR′,—OR′, —OSiR′3 or —PR′2 radicals in which R′ is one of a halogen atom, aC1-C₁₀ alkyl group, or a C6-C10 aryl group; or two or more adjacentradicals R⁵ to R⁷ together with the atoms connecting them can form oneor more rings (preferably R³ is methyl, ethyl or butyl), and adjacentradicals R¹¹ and R¹² can form one or more saturated or aromatic rings(preferably R¹¹ and R¹² combine with the phenyl ring to form asubstituted or unsubstituted naphthyl group), in an advantageousembodiment, R⁹ and R¹¹ are a C1 to C20 hydrocarbyl group, or a C3 to C12alkyl group, advantageously a t-butyl group;

R¹³ is selected from:

—B(R¹⁴)—, —Al(R¹⁴)—, —Ge—, —Sn—, —O—, —S—, —SO—, —SO2—, —N(R¹⁴)—, —CO—,—P(R¹⁴)—, —P(O)(R¹⁴)—, —B(NR¹⁴R¹⁵)— and —B[N(SiR¹⁴R¹⁵R¹⁶)2]-, R¹⁴, R¹⁵and R¹⁶ are each independently selected from hydrogen, halogen, C1-C20alkyl groups, C6-C30 aryl groups, C1-C20 alkoxy groups, C2-C20 alkenylgroups, C7-C40 arylalkyl groups, C8-C40 arylalkenyl groups and C7-C40alkylaryl groups, or R¹⁴ and R¹⁵, together with the atom(s) connectingthem, form a ring; and M³ is selected from carbon, silicon, germaniumand tin, or R¹³ is represented by the formula:

wherein R¹⁷ to R²⁴ are as defined for R¹ and R², or two or more adjacentradicals R¹⁷ to R²⁴, including R²⁰ and R²¹, together with the atomsconnecting them form one or more rings; M² is carbon, silicon,germanium, or tin (preferably R¹³ is dimethyl silyl or diphenylsilyl).

Particularly useful catalyst compounds to make vinyl terminatedisotactic propylene macromonomers (preferably crystalline, e.g. havingat least 40% crystallinity) include those represented by the formula:rac-Me₂Si-bis(2-R-indenyl)MX₂ or rac-Me₂Si-bis(2-R,4-Ph-indenyl)MX₂,where R is an alkyl group (such as methyl), Ph is phenyl or substitutedphenyl, M is Hf, Zr or Ti, and X is a halogen or alkyl group (such as Clor methyl). Examples includedimethylsilyl-bis(2-methyl-indenyl)zirconium dimethyl (or dichloride),dimethylsilyl-bis(2-methyl,4-phenyl-indenyl)zirconium dimethyl (ordichloride),dimethylsilyl-bis(2-methyl,4-(3′,5′-di-t-butyl-phenyl)-indenyl)zirconiumdimethyl (or dichloride),dimethylsilyl-bis(2-methyl,4-naphthyl-indenyl)zirconium dimethyl (ordichloride), anddimethylsilyl-bis(2-methyl,4-(3′,5′-di-t-butyl-naphthyl)-indenyl)zirconiumdimethyl (or dichloride), or alternately the compounds where zirconiumis replaced by hafnium. Other useful catalysts compounds include:(CpMe₄)(1,3-dimethyl Ind)Hf Me₂; (CpMe₄)(1-iPr Ind)Hf Me₂;(CpMe₄)(1-iPr,3-nPr Ind)Hf Me₂; (CpMe₅)((1,3-dimethyl Ind)Hf Me₂;(CpMe₅)((1,3-di-n-propyl Ind)Hf Me₂; (CpMe₅)((1,2,3-trimethyl Ind)HfMe_(e), where Cp=cyclopentadienyl, Ind=indenyl, Me=methyl,iPr=isopropyl, and nPr=n-propyl.

In a preferred embodiment, the oligomers i) to iv) can be produced usinga catalyst system comprising an activator and a catalyst compoundrepresented by the following formulae:

where

-   Hf is hafnium;-   each X is, independently, selected from the group consisting of    hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides,    amides, alkoxides, sulfides, phosphides, halogens, dienes, amines,    phosphines, ethers, or a combination thereof, preferably methyl,    ethyl, propyl, butyl, phenyl, benzyl, chloride, bromide, iodide,    (alternately two X's may form a part of a fused ring or a ring    system);-   each Q is, independently carbon or a heteroatom, preferably C, N, P,    S (preferably at least one Q is a heteroatom, alternately at least    two Q's are the same or different heteroatoms, alternately at least    three Q's are the same or different heteroatoms, alternately at    least four Q's are the same or different heteroatoms);-   each R¹ is, independently, hydrogen or a C₁ to C₈ alkyl group,    preferably a C₁ to C₈ linear alkyl group, preferably methyl ethyl,    propyl, butyl, pentyl, hexyl, heptyl or octyl, R¹ may the same or    different as R²;-   each R² is, independently, hydrogen or a C₁ to C₈ alkyl group,    preferably a C₁ to C₈ linear alkyl group, preferably methyl ethyl,    propyl, butyl, pentyl, hexyl, heptyl or octyl, provided that at    least one of R¹ or R² is not hydrogen, preferably both of R¹ and R²    are not hydrogen, preferably R¹ and/or R² are not branched;-   each R³ is, independently, hydrogen, or a substituted or    unsubstituted hydrocarbyl group having from 1 to 8 carbon atoms,    preferably 1 to 6 carbon atoms, preferably a substituted or    unsubstituted C₁ to C₈ linear alkyl group, preferably methyl ethyl,    propyl, butyl, pentyl, hexyl, heptyl, octyl, provided however that    at least three R³ groups are not hydrogen (alternately four R³    groups are not hydrogen, alternately five R³ groups are not    hydrogen);-   {Alternately, when the catalyst compound is to used to make the    homo-oligomer then each R³ is, independently, hydrogen, or a    substituted or unsubstituted hydrocarbyl group having from 1 to 8    carbon atoms, preferably 1 to 6 carbon atoms, preferably a    substituted or unsubstituted C₁ to C₈ linear alkyl group, preferably    methyl ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, provided    however that: 1) all five R³ groups are methyl, or 2) four R³ groups    are not hydrogen and at least one R³ group is a C₂ to C₈ substituted    or unsubstituted hydrocarbyl (preferably at least two, three, four    or five R³ groups are a C₂ to C₈ substituted or unsubstituted    hydrocarbyl)};-   each R⁴ is, independently, hydrogen or a substituted or    unsubstituted hydrocarbyl group, a heteroatom or heteroatom    containing group, preferably a substituted or unsubstituted    hydrocarbyl group having from 1 to 20 carbon atoms, preferably 1 to    8 carbon atoms, preferably a substituted or unsubstituted C₁ to C₈    linear alkyl group, preferably methyl ethyl, propyl, butyl, pentyl,    hexyl, heptyl, octyl, substituted phenyl (such as propyl phenyl),    phenyl, silyl, substituted silyl, (such as CH₂SiR′, where R′ is a C₁    to C₁₂ hydrocarbyl, such as methyl, ethyl, propyl, butyl, phenyl);-   R⁵ is hydrogen or a C₁ to C₈ alkyl group, preferably a C₁ to C₈    linear alkyl group, preferably methyl, ethyl, propyl, butyl, pentyl,    hexyl, heptyl or octyl;-   R⁶ is hydrogen or a C₁ to C₈ alkyl group, preferably a C₁ to C₈    linear alkyl group, preferably methyl, ethyl, propyl, butyl, pentyl,    hexyl, heptyl or octyl;-   each R⁷ is, independently, hydrogen, or a C₁ to C₈ alkyl group,    preferably a C₁ to C₈ linear alkyl group, preferably methyl ethyl,    propyl, butyl, pentyl, hexyl, heptyl or octyl, provided however that    at least seven R⁷ groups are not hydrogen, alternately at least    eight R⁷ groups are not hydrogen, alternately all R⁷ groups are not    hydrogen, (preferably the R⁷ groups at the 3 and 4 positions on each    Cp ring of Formula IV are not hydrogen);-   N is nitrogen;-   T is a bridge, preferably, Si or Ge, preferably Si;-   each R^(a), is independently, hydrogen, halogen or a C₁ to C₂₀    hydrocarbyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl,    heptyl, octyl, phenyl, benzyl, substituted phenyl, and two R^(a) can    form a cyclic structure including aromatic, partially saturated, or    saturated cyclic or fused ring system; and further provided that any    two adjacent R groups may form a fused ring or multicenter fused    ring system where the rings may be aromatic, partially saturated or    saturated.

The term “substituted” means that a hydrogen group has been replacedwith a hydrocarbyl group, a heteroatom or a heteroatom containing group.For example methyl cyclopentadiene (Cp) is a Cp group substituted with amethyl group and ethyl alcohol is an ethyl group substituted with an —OHgroup.

In an alternate embodiment, at least one R⁴ group is not hydrogen,alternately at least two R⁴ groups are not hydrogen, alternately atleast three R⁴ groups are not hydrogen, alternately at least four R⁴groups are not hydrogen, alternately all R⁴ groups are not hydrogen.

Catalyst compounds that are particularly useful include one or more of:

-   (1,3-Dimethylindenyl)(pentamethylcyclopentadienyl)Hafniumdimethyl,-   (1,3,4,7-Tetramethylindenyl)(pentamethylcyclopentadienyl)Hafniumdimethyl,-   (1,3-Dimethylindenyl)(tetramethylcyclopentadienyl)Hafniumdimethyl,-   (1,3-Diethylindenyl)(pentamethylcyclopentadienyl)Hafniumdimethyl,-   (1,3-Dipropylindenyl)(pentamethylcyclopentadienyl)Hafniumdimethyl,-   (1-Methyl,3-propyllindenyl)(pentamethylcyclopentadienyl)Hafniumdimethyl,-   (1,3-Dimethylindenyl)(tetramethylpropylcyclopentadienyl)Hafniumdimethyl,-   (1,2,3-Trimethylindenyl)(pentamethylcyclopentadienyl)Hafniumdimethyl,-   (1,3-Dimethylbenzindenyl)(pentamethyl    cyclopentadienyl)Hafniumdimethyl,-   (2,7-Bis    t-butylfluorenyl)(pentamethylcyclopentadienyl)Hafniumdimethyl,-   (9-Methylfluorenyl)(pentamethylcyclopentadienyl)Hafniumdimethyl,-   (2,7,9-Trimethylfluorenyl)(pentamethylcyclopentadienyl)Hafniumdimethyl,-   μ-Dihydrosilyl(bis tetramethylcyclopentadienyl)Hafniumdimethyl,-   μ-Dihydrosilyl(bis tetramethylcyclopentadienyl)Hafniumdimethyl,-   μ-Dimethylsilyl(tetramethylcyclopentadienyl)(3-propyltrimethylcyclopentadienyl)    Hafniumdimethyl,-   and μ-Dicyclopropylsilyl(bis    tetramethylcyclopentadienyl)Hafniumdimethyl.

In an alternate embodiment, the “dimethyl” after the transition metal inthe list of catalyst compounds above is replaced with a dihalide (suchas dichloride or difluoride) or a bisphenoxide, particularly for usewith an alumoxane activator.

Activators

Useful activators include alumoxanes and non-coordinating anionactivators, whether neutral or ionic. Examples include alkylalumoxane,such as methylalumoxane, ethyl alumoxane, butyl alumoxane, isobutylalumoxane; modified alumoxanes such as modified alkyl alumoxanes,including modified methyl alumoxane and the like. Mixtures of differentalumoxanes and modified alumoxanes may also be used. Alumoxanes may beproduced by the hydrolysis of the respective trialkylaluminum compound.MMAO may be produced by the hydrolysis of trimethylaluminum and a highertrialkylaluminum such as triisobutylaluminum. MMAO's are generally moresoluble in aliphatic solvents and more stable during storage. There area variety of methods for preparing alumoxane and modified alumoxanes,non-limiting examples of which are described in U.S. Pat. Nos.4,665,208, 4,952,540, 5,091,352, 5,206,199, 5,204,419, 4,874,734,4,924,018, 4,908,463, 4,968,827, 5,308,815, 5,329,032, 5,248,801,5,235,081, 5,157,137, 5,103,031, 5,391,793, 5,391,529, 5,693,838,5,731,253, 5,731,451, 5,744,656, 5,847,177, 5,854,166, 5,856,256 and5,939,346 and European publications EP-A-0 561 476, EP-B1-0 279 586,EP-A-0 594-218 and EP-B1-0 586 665, and PCT publications WO 94/10180 andWO 99/15534, all of which are herein fully incorporated by reference. Itmay be preferable to use a visually clear methylalumoxane. A cloudy orgelled alumoxane can be filtered to produce a clear solution or clearalumoxane can be decanted from the cloudy solution. Another usefulalumoxane is a modified methyl alumoxane (MMAO) cocatalyst type 3A(commercially available from Akzo Chemicals, Inc. under the trade nameModified Methylalumoxane type 3A, covered under U.S. Pat. No.5,041,584). When the activator is an alumoxane (modified or unmodified),some embodiments select the maximum amount of activator at a 5000-foldmolar excess Al/M over the catalyst precursor (per metal catalyticsite). The minimum activator-to-catalyst-precursor is typically a 1:1molar ratio.

Aluminum alkyl or organoaluminum compounds which may be utilized asactivators (or scavengers) herein include trimethylaluminum,triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum,tri-n-octylaluminum and the like. If used as scavengers they aretypically present at a ratio of 10:1 up to 100:1 mole:mole.

In another embodiment, the activator may be an ionizing orstoichiometric activator, neutral or ionic, such as tri (n-butyl)ammonium tetrakis (pentafluorophenyl) boron, a trisperfluorophenyl boronmetalloid precursor or a trisperfluoronaphtyl boron metalloid precursor,polyhalogenated heteroborane anions (WO 98/43983), boric acid (U.S. Pat.No. 5,942,459) or combination thereof. It is also within the scope ofthis invention to use neutral or ionic activators alone or incombination with alumoxane or modified alumoxane activators.

Examples of neutral stoichiometric activators include tri-substitutedboron, tellurium, aluminum, gallium and indium or mixtures thereof. Thethree substituent groups are each independently selected from alkyls,alkenyls, halogen, substituted alkyls, aryls, arylhalides, alkoxy andhalides. Preferably, the three groups are independently selected fromhalogen, mono or multicyclic (including halosubstituted) aryls, alkyls,and alkenyl compounds and mixtures thereof, preferred are alkenyl groupshaving 1 to 20 carbon atoms, alkyl groups having 1 to 20 carbon atoms,alkoxy groups having 1 to 20 carbon atoms and aryl groups having 3 to 20carbon atoms (including substituted aryls). More preferably, the threegroups are alkyls having 1 to 4 carbon groups, phenyl, napthyl ormixtures thereof. Even more preferably, the three groups arehalogenated, preferably fluorinated, aryl groups. Most preferably, theneutral stoichiometric activator is trisperfluorophenyl boron ortrisperfluoronapthyl boron.

Ionic stoichiometric activator compounds may contain an active proton,or some other cation associated with, but not coordinated to, or onlyloosely coordinated to, the remaining ion of the ionizing compound. Suchcompounds and the like are described in European publications EP-A-0 570982, EP-A-0 520 732, EP-A-0 495 375, EP-B1-0 500 944, EP-A-0 277 003 andEP-A-0 277 004, and U.S. Pat. Nos. 5,153,157, 5,198,401, 5,066,741,5,206,197, 5,241,025, 5,384,299 and 5,502,124 and U.S. patentapplication Ser. No. 08/285,380, filed Aug. 3, 1994, all of which areherein fully incorporated by reference.

Ionic catalysts can be preparedly reacting a transition metal compoundwith some neutral Lewis acids, such as B(C₆F₆)₃, which upon reactionwith the hydrolyzable ligand (X) of the transition metal compound formsan anion, such as ([B(C₆F₅)₃(X)]⁻), which stabilizes the cationictransition metal species generated by the reaction. The catalysts canbe, and preferably are, prepared with activator components which areionic compounds or compositions. However preparation of activatorsutilizing neutral compounds is also contemplated by this invention.

Compounds useful as an activator component in the preparation of theionic catalyst systems used in the process of this invention comprise acation, which is preferably a Bronsted acid capable of donating aproton, and a compatible non-coordinating anion which anion isrelatively large (bulky), capable of stabilizing the active catalystspecies (the Group 4 cation) which is formed when the two compounds arecombined and said anion will be sufficiently labile to be displaced byolefinic diolefinic and acetylenically unsaturated substrates or otherneutral Lewis bases such as ethers, nitriles and the like. Two classesof compatible non-coordinating anions have been disclosed in EPA 277,003and EPA 277,004 published 1988: 1) anionic coordination complexescomprising a plurality of lipophilic radicals covalently coordinated toand shielding a central charge-bearing metal or metalloid core, and 2)anions comprising a plurality of boron atoms such as carboranes,metallacarboranes and boranes.

In a preferred embodiment, the stoichiometric activators include acation and an anion component, and may be represented by the followingformula:(L-H)_(d) ⁺(A^(d−))wherein L is an neutral Lewis base;

-   H is hydrogen;-   (L-H)⁺ is a Bronsted acid-   A^(d−) is a non-coordinating anion having the charge d−-   d is an integer from 1, 2 or 3.

The cation component, (L-H)_(d) ⁺ may include Bronsted acids such asprotons or protonated Lewis bases or reducible Lewis acids capable ofprotonating or abstracting a moiety, such as an alkyl or aryl, from thebulky ligand metallocene containing transition metal catalyst precursor,resulting in a cationic transition metal species.

The activating cation (L-H)_(d) ⁺ may be a Bronsted acid, capable ofdonating a proton to the transition metal catalytic precursor resultingin a transition metal cation, including ammoniums, oxoniums,phosphoniums, silyliums, and mixtures thereof, preferably ammoniums ofmethylamine, aniline, dimethylamine, diethylamine, N-methylaniline,diphenylamine, trimethylamine, triethylamine, N,N-dimethylaniline,methyldiphenylamine, pyridine, p-bromo N,N-dimethylaniline,p-nitro-N,N-dimethylaniline, phosphoniums from triethylphosphine,triphenylphosphine, and diphenylphosphine, oxomiuns from ethers such asdimethyl ether diethyl ether, tetrahydrofuran and dioxane, sulfoniumsfrom thioethers, such as diethyl thioethers and tetrahydrothiophene, andmixtures thereof. The activating cation (L-H)_(d) ⁺ may also be a moietysuch as silver, tropylium, carbeniums, ferroceniums and mixtures,preferably carboniums and ferroceniums. Most preferably (L-H)_(d) ⁺ istriphenyl carbonium.

The anion component A^(d−) include those having the formula[M^(k+)Q_(n)]^(d−) wherein k is an integer from 1 to 3; n is 2, 3, 4, 5or 6; n−k=d; M is an element selected from Group 13 of the PeriodicTable of the Elements, preferably boron or aluminum, and Q isindependently a hydride, bridged or unbridged dialkylamido, halide,alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl,substituted halocarbyl, and halosubstituted-hydrocarbyl radicals, said Qhaving up to 20 carbon atoms with the proviso that in not more than 1occurrence is Q a halide. Preferably, each Q is a fluorinatedhydrocarbyl group having 1 to 20 carbon atoms, more preferably each Q isa fluorinated aryl group, and most preferably each Q is a pentafluorylaryl group. Examples of suitable A^(d−) also include diboron compoundsas disclosed in U.S. Pat. No. 5,447,895, which is fully incorporatedherein by reference.

Examples of useful activators include: is N,N-dimethylaniliniumtetra(perfluorophenyl)borate, N,N-dimethylaniliniumtetrakis(perfluoronapthyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbeniumtetrakis(perfluoronapthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, and triphenylcarbeniumtetra(perfluorophenyl)borate.

The term “non-coordinating anion” (NCA) means an anion which either doesnot coordinate to said cation or which is only weakly coordinated tosaid cation thereby remaining sufficiently labile to be displaced by aneutral Lewis base. “Compatible” non-coordinating anions are those whichare not degraded to neutrality when the initially formed complexdecomposes. Further, the anion will not transfer an anionic substituentor fragment to the cation so as to cause it to form a neutral fourcoordinate metallocene compound and a neutral by-product from the anion.Non-coordinating anions useful in accordance with this invention arethose that are compatible, stabilize the metallocene cation in the senseof balancing its ionic charge at +1, yet retain sufficient lability topermit displacement by an ethylenically or acetylenically unsaturatedmonomer during polymerization. These types of cocatalysts sometimes usetri-isobutyl aluminum or tri-octyl aluminum as a scavenger.

Invention process also can employ cocatalyst compounds or activatorcompounds that are initially neutral Lewis acids but form a cationicmetal complex and a noncoordinating anion, or a zwitterionic complexupon reaction with the invention compounds. For example,tris(pentafluorophenyl) boron or aluminum act to abstract a hydrocarbylor hydride ligand to yield an invention cationic metal complex andstabilizing noncoordinating anion, see EP-A-0 427 697 and EP-A-0 520 732for illustrations of analogous Group-4 metallocene compounds. Also, seethe methods and compounds of EP-A-0 495 375. For formation ofzwitterionic complexes using analogous Group 4 compounds, see U.S. Pat.Nos. 5,624,878; 5,486,632; and 5,527,929.

When the cations of noncoordinating anion precursors are Bronsted acidssuch as protons or protonated Lewis bases (excluding water), orreducible Lewis acids such as ferrocenium or silver cations, or alkalior alkaline earth metal cations such as those of sodium, magnesium orlithium, the catalyst-precursor-to-activator molar ratio may be anyratio. Combinations of the described activator compounds may also beused for activation. For example, tris(perfluorophenyl) boron can beused with methylalumoxane.

In general the catalyst compounds and the activator are combined inratios of about 1:10,000 to about 10:1. When alumoxane or aluminum alkylactivators are used, the catalyst-to-activator molar ratio may be from1:5000 to 10:1, alternatively from 1:1000 to 10:1; alternatively, 1:500to 2:1; or 1:300 to 1:1. When ionizing activators are used, thecatalyst-to-activator molar ratio is from 10:1 to 1:10; 5:1 to 1:5; 2:1to 1:2; or 1.2:1 to 1:1. Multiple activators may be used, includingusing mixes of alumoxanes or aluminum alkyls with ionizing activators.

In an alternate embodiment, other additives may be used, such as diethylzinc, in combination with the catalyst compounds and activators.

Polymerization Processes to Make Macromonomer

The catalysts and catalyst systems described above may be used toproduce the macromonomers in a solution, bulk, gas or slurrypolymerization process or a combination thereof, preferably a solutionphase (preferably a continuous solution phase) polymerization process.(For convenience the processes described herein will referred to aspolymerizations, even though they may produce an oligomer). Asupercritical process can also be used, preferably a supercriticalprocess above the melting point of the macromonomers being produced isused, preferably a supercritical process above the cloud point of thepolymerization system is used. For more information on the details ofthe supercritical process (including definitions of cloud point andpolymerization system) please see WO 2004/026921. In another embodiment,the processes disclosed in U.S. Pat. No. 7,432,336 (incorporated byreference herein) may be used. For example a continuous polymerizationsmay be carried out in a stainless steel continuous autoclave reactorequipped with a stirrer, steam heating/water cooling element and apressure controller. Solvent, macromonomer and comonomer (if any) aretypically first chilled to −15° C. prior to entering a manifold, andthen pumped into the reactor. The preactivated catalyst solution is fedinto the reactor from a dry box through metering pumps in a separateline. Solvent (such as hexanes) are pumped into the reactor at a desiredrate to control the residence time.

In one embodiment, the catalyst systems described herein may be used incombination with one or more of monomers having from 2 to 30 carbonatoms, preferably 2-12 carbon atoms, and more preferably 2 to 8 carbonatoms in one or more reactors in series or in parallel to produce themacromonomers described herein. (Preferred monomers include one or moreof ethylene, propylene, butene-1, pentene-1, 4-methyl-pentene-1,hexene-1, octene-1, decene-1,4-methyl-pentene-1, 3-methyl-pentene-1, ora combination thereof.) The catalyst component and activator may bedelivered as a solution or slurry, either separately to the reactor,activated in-line just prior to the reactor, or preactivated and pumpedas an activated solution or slurry to the reactor. The polymerizationsare carried out in either single reactor operation, in which monomer,comonomers, catalyst/activator, scavenger, and optional modifiers areadded continuously to a single reactor or in series reactor operation,in which the above components are added to each of two or more reactorsconnected in series. The catalyst components can be added to the firstreactor in the series. The catalyst component may also be added to bothreactors, with one component being added to first reaction and anothercomponent to other reactors. Typically the polymerizations occur at atemperature of 30 to 150° C., preferably 35 to 120° C., preferably 40 to100° C., alternately 40 to 150° C., alternately 45 to 120° C.,alternately 50 to 100° C. Typically the polymerizations occur at aresidence time of 1 second to 3 hours, preferably 1 minutes to 90minutes, preferably 1 minute to 30 minutes, preferably 1 minute to 15minutes.

The polymerization may occur in gas phase, such as, in a fluidized gasbed process used for producing polymers, where a gaseous streamcontaining one or more monomers is continuously cycled through afluidized bed in the presence of a catalyst under reactive conditions.The gaseous stream is withdrawn from the fluidized bed and recycled backinto the reactor. Simultaneously, polymer product is withdrawn from thereactor and fresh monomer is added to replace the polymerized monomer.(See for example U.S. Pat. Nos. 4,543,399, 4,588,790, 5,028,670,5,317,036, 5,352,749, 5,405,922, 5,436,304, 5,453,471, 5,462,999,5,616,661 and 5,668,228 all of which are fully incorporated herein byreference.)

In some cases, slurry phase polymerization system may also be usedherein. A slurry polymerization process generally operates between 1 toabout 50 atmosphere pressure range (15 psi to 735 psi, 103 kPa to 5068kPa) or even greater and temperatures in the range of 0° C. to about120° C. In a slurry polymerization, a suspension of solid, particulatepolymer is formed in a liquid polymerization diluent medium to whichmonomer and comonomers along with catalyst are added. The suspensionincluding diluent is intermittently or continuously removed from thereactor where the volatile components are separated from the polymer andrecycled, optionally after a distillation, to the reactor. The liquiddiluent employed in the polymerization medium is typically an alkanehaving from 3 to 7 carbon atoms, preferably a branched alkane. Themedium employed should be liquid under the conditions of polymerizationand relatively inert. When a propane medium is used the process must beoperated above the reaction diluent critical temperature and pressure.Preferably, a hexane or an isobutane medium is employed.

In one embodiment, a preferred polymerization technique useful in theinvention is referred to as a particle form polymerization, or a slurryprocess where the temperature is kept below the temperature at which thepolymer goes into solution. Such technique is well known in the art, anddescribed in for instance U.S. Pat. No. 3,248,179 which is fullyincorporated herein by reference. The preferred temperature in theparticle form process is within the range of about 85° C. to about 110°C. Two preferred polymerization methods for the slurry process are thoseemploying a loop reactor and those utilizing a plurality of stirredreactors in series, parallel, or combinations thereof. Non-limitingexamples of slurry processes include continuous loop or stirred tankprocesses. Also, other examples of slurry processes are described inU.S. Pat. No. 4,613,484, which is herein fully incorporated byreference.

In another embodiment, the slurry process is carried out continuously ina loop reactor. The catalyst, as a slurry in isobutane or as a dry freeflowing powder, is injected regularly to the reactor loop, which isitself filled with circulating slurry of growing polymer particles in adiluent of isobutane containing monomer and comonomer. Hydrogen,optionally, may be added as a molecular weight control. (In oneembodiment 500 ppm or less of hydrogen is added, or 400 ppm or less or300 ppm or less. In other embodiments at least 50 ppm of hydrogen isadded, or 100 ppm or more, or 150 ppm or more.)

A homogeneous (solution or bulk) batch or continuous process may also beused herein. Generally this involves polymerization in a continuousreactor in which the polymer formed and the starting monomer andcatalyst materials supplied, are agitated to reduce or avoidconcentration gradients. Suitable processes operate above the meltingpoint of the polymers at high pressures, from 1 to 3000 bar (10-30,000MPa), in which the monomer acts as diluent or in solution polymerizationusing a solvent. The reactor temperature depends on the catalyst used.In general, the reactor temperature preferably can vary between about30° C. and about 160° C., more preferably from about 40° C. to about120° C., and most preferably from about 50° C. to about 110° C. Inparallel reactor operation, the temperatures of the two reactors areindependent. The pressure can vary from about 1 mm Hg to 2500 bar(25,000 MPa), preferably from 0.1 bar to 1600 bar (1-16,000 MPa), mostpreferably from 1.0 to 500 bar (10-5000 MPa).

Each of these processes may also be employed in single reactor, parallelor series reactor configurations, in batch or continuous mode. Theliquid processes comprise contacting olefin monomers with the abovedescribed catalyst system in a suitable diluent or solvent and allowingsaid monomers to react for a sufficient time to produce the desiredpolymers. Hydrocarbon solvents are suitable, both aliphatic andaromatic. Alkanes, such as hexane, pentane, isopentane, and octane, arepreferred.

The process can be carried out in a continuous stirred tank reactor,batch reactor or plug flow reactor, or more than one reactor operated inseries or parallel. These reactors may have or may not have internalcooling or heating and the monomer feed may or may not be refrigerated.See the general disclosure of U.S. Pat. No. 5,001,205 for generalprocess conditions. See also, international application WO 96/33227 andWO 97/22639. All documents are incorporated by reference for US purposesfor description of polymerization processes, metallocene selection anduseful scavenging compounds.

For more information on the processes to produce oligomers i) to vi)please see U.S. Ser. No. 12/143,663, filed Jun. 20, 2008.

In a preferred embodiment, the propylene co-oligomer of oligomers i) tovi) may be produce by a homogenous process, said process havingproductivity of at least 4.5×10³ g/mmol/hr, wherein the processcomprises:

contacting, at a temperature of from 35° C. to 150° C., propylene, 0.1to 70 mol % ethylene and from 0 to about 5 wt % hydrogen in the presenceof a catalyst system comprising an activator and at least onemetallocene compound represented by the formulae I, II, II or IV above,where: Hf is hafnium; each X is, independently, selected from the groupconsisting of hydrocarbyl radicals having from 1 to 20 carbon atoms,hydrides, amides, alkoxides, sulfides, phosphides, halogens, dienes,amines, phosphines, ethers, or a combination thereof, preferably methyl,ethyl, propyl, butyl, phenyl, benzyl, chloride, bromide, iodide,(alternately two X's may form a part of a fused ring or a ring system);each Q is, independently carbon or a heteroatom, preferably C, N, P, S(preferably at least one Q is a heteroatom, alternately at least two Q'sare the same or different heteroatoms, alternately at least three Q'sare the same or different heteroatoms, alternately at least four Q's arethe same or different heteroatoms); each R¹ is, independently, a C₁ toC₈ alkyl group, preferably a C₁ to C₈ linear alkyl group, preferablymethyl ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl, R¹ may thesame or different as R²; each R² is, independently, a C₁ to C₈ alkylgroup, preferably a C₁ to C₈ linear alkyl group, preferably methylethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl, preferably R¹and/or R² are not branched;

each R³ is, independently, hydrogen, or a substituted or unsubstitutedhydrocarbyl group having from 1 to 8 carbon atoms, preferably 1 to 6carbon atoms, preferably a substituted or unsubstituted C₁ to C₈ linearalkyl group, preferably methyl ethyl, propyl, butyl, pentyl, hexyl,heptyl, octyl, provided however that at least three R³ groups are nothydrogen (alternately four R³ groups are not hydrogen, alternately fiveR³ groups are not hydrogen); each R⁴ is, independently, hydrogen or asubstituted or unsubstituted hydrocarbyl group, a heteroatom orheteroatom containing group, preferably a substituted or unsubstitutedhydrocarbyl group having from 1 to 20 carbon atoms, preferably 1 to 8carbon atoms, preferably a substituted or unsubstituted C₁ to C₈ linearalkyl group, preferably methyl ethyl, propyl, butyl, pentyl, hexyl,heptyl, octyl, substituted phenyl (such as propyl phenyl), phenyl,silyl, substituted silyl, (such as CH₂SiR′, where R′ is a C₁ to C₁₂hydrocarbyl, such as methyl, ethyl, propyl, butyl, phenyl); R⁵ ishydrogen or a C₁ to C₈ alkyl group, preferably a C₁ to C₈ linear alkylgroup, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl oroctyl; R⁶ is hydrogen or a C₁ to C₈ alkyl group, preferably a C₁ to C₈linear alkyl group, preferably methyl, ethyl, propyl, butyl, pentyl,hexyl, heptyl or octyl; each R⁷ is, independently, hydrogen, or a C₁ toC₈ alkyl group, preferably a C₁ to C₈ linear alkyl group, preferablymethyl ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl, providedhowever that at least seven R⁷ groups are not hydrogen, alternately atleast eight R⁷ groups are not hydrogen, alternately all R⁷ groups arenot hydrogen, (preferably the R⁷ groups at the 3 and 4 positions on eachCp ring of Formula IV are not hydrogen); N is nitrogen; T is a bridge,preferably, Si or Ge, preferably Si; each R^(a), is independently,hydrogen, halogen or a C₁ to C₂₀ hydrocarbyl, such as methyl, ethyl,propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl, benzyl, substitutedphenyl, and two R^(a) can form a cyclic structure including aromatic,partially saturated, or saturated cyclic or fused ring system; andfurther provided that any two adjacent R groups may form a fused ring ormulticenter fused ring system where the rings may be aromatic, partiallysaturated or saturated.

In a preferred embodiment, the propylene homo-oligomer of oligomers i)to vi) may be produce by a homogenous process, said process having aproductivity of at least 4.5×10⁶ g/mol/min, wherein the processcomprises:

contacting, at a temperature of from 30° C. to 120° C., propylene, 0 mol% comonomer and from 0 to about 5 wt % hydrogen in the presence of acatalyst system comprising an activator and at least one metallocenecompound represented by the formulae I, II, III or IV disclosed abovewherein: Hf is hafnium; each X is, independently, selected from thegroup consisting of hydrocarbyl radicals having from 1 to 20 carbonatoms, hydrides, amides, alkoxides, sulfides, phosphides, halogens,dienes, amines, phosphines, ethers, or a combination thereof, preferablymethyl, ethyl, propyl, butyl, phenyl, benzyl, chloride, bromide, iodide,(alternately two X's may form a part of a fused ring or a ring system);each Q is, independently carbon or a heteroatom, preferably C, N, P, S(preferably at least one Q is a heteroatom, alternately at least two Q'sare the same or different heteroatoms, alternately at least three Q'sare the same or different heteroatoms, alternately at least four Q's arethe same or different heteroatoms); each R¹ is, independently, a C₁ toC₈ alkyl group, preferably a C₁ to C₈ linear alkyl group, preferablymethyl ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl, R¹ may thesame or different as R²; each R² is, independently, a C₁ to C₈ alkylgroup, preferably a C₁ to C₈ linear alkyl group, preferably methylethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl, preferably R¹and/or R² are not branched; each R³ is, independently, hydrogen, or asubstituted or unsubstituted hydrocarbyl group having from 1 to 8 carbonatoms, preferably 1 to 6 carbon atoms, preferably a substituted orunsubstituted C₁ to C₈ linear alkyl group, preferably methyl ethyl,propyl, butyl, pentyl, hexyl, heptyl, octyl, provided however that: 1)all five R³ groups are methyl, or 2) four R³ groups are not hydrogen andat least one R³ group is a C₂ to C₈ substituted or unsubstitutedhydrocarbyl (preferably at least two, three, four or five R³ groups area C₂ to C₈ substituted or unsubstituted hydrocarbyl); each R⁴ is,independently, hydrogen or a substituted or unsubstituted hydrocarbylgroup, a heteroatom or heteroatom containing group, preferably asubstituted or unsubstituted hydrocarbyl group having from 1 to 20carbon atoms, preferably 1 to 8 carbon atoms, preferably a substitutedor unsubstituted C₁ to C₈ linear alkyl group, preferably methyl ethyl,propyl, butyl, pentyl, hexyl, heptyl, octyl, substituted phenyl (such aspropyl phenyl), phenyl, silyl, substituted silyl, (such as CH₂SiR′,where R′ is a C₁ to C₁₂ hydrocarbyl, such as methyl, ethyl, propyl,butyl, phenyl); R⁵ is hydrogen or a C₁ to C₈ alkyl group, preferably aC₁ to C₈ linear alkyl group, preferably methyl, ethyl, propyl, butyl,pentyl, hexyl, heptyl or octyl; R⁶ is hydrogen or a C₁ to C₈ alkylgroup, preferably a C₁ to C₈ linear alkyl group, preferably methyl,ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl; each R⁷ is,independently, hydrogen, or a C₁ to C₈ alkyl group, preferably a C₁ toC₈ linear alkyl group, preferably methyl ethyl, propyl, butyl, pentyl,hexyl, heptyl or octyl, provided however that at least seven R⁷ groupsare not hydrogen, alternately at least eight R⁷ groups are not hydrogen,alternately all R⁷ groups are not hydrogen, (preferably the R⁷ groups atthe 3 and 4 positions on each Cp ring of Formula IV are not hydrogen); Nis nitrogen;

T is a bridge, preferably, Si or Ge, preferably Si; each R^(a), isindependently, hydrogen, halogen or a C₁ to C₂₀ hydrocarbyl, such asmethyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl,benzyl, substituted phenyl, and two R^(a) can form a cyclic structureincluding aromatic, partially saturated, or saturated cyclic or fusedring system; and further provided that any two adjacent R groups mayform a fused ring or multicenter fused ring system where the rings maybe aromatic, partially saturated or saturated.

In a particularly preferred embodiment, the macromonomer is made in afirst reactor then transferred to a second reactor, reaction zone, orreaction extruder where it is polymerized to form the polymacromonomer.

Process to Polymerize Macromonomer to Make Polymacromonomer

In another embodiment this invention relates to a process to producepolymacromonomer comprising contacting macromonomer and from 0 to 40 wt% of comonomer of C₂ to C₁₈olefin (preferably alpha-olefin) in thefeedstream (preferably from 0 to 30 wt %, preferably from 0 to 20 wt %,preferably from 0 to 10 wt %, preferably from 0 to 5 wt %, preferablyfrom 0.5 to 1 wt % of C₂ to C₁₈comonomer) with a catalyst system capableof polymerizing vinyl terminated macromonomer (preferably wherein themacromonomer is as described above (preferably having: 1) from 20 to1500 carbon atoms, 2) an Mn of 280 or more, 3) an Mw of 450 or more, 4)an Mz of 600 or more, 5) an Mw/Mn of 1.5 or more, 6) 70% or more vinyltermination, 7) less than 10 wt % styrenic monomer, and 8) optionally, amelting point Tm of 60° C. or more (or optionally virtually amorphous);at a temperature of 60 to 130° C. (alternately from 70 to 120° C.,alternately from 75 to 115° C.)) and at reaction time of from 1 minuteto 90 minutes (alternately from 1 to 60 min, alternately from 1 to 45min), wherein the molar ratio of all comonomer present in the reactor toall macromonomer present in the reaction zone is 3:1 or less, preferably2:1 or less, preferably 1:1 or less. In a preferred embodiment theconsumption of macromonomer is 70 wt % or more, preferably 75% or more,preferably 80% or more, preferably 90% or more, based upon the weight ofmacromonomer entering the reactor in the feedstream as compared to theamount of macromonomer recovered after the polymerization at the exit ofthe reactor, as described above.

The catalysts and catalyst systems described below may be used toproduce the polymacromonomers in a solution, bulk, gas or slurrypolymerization process or a combination thereof, preferably a solutionphase or slurry phase polymerization process. The general polymerizationprocess and conditions described above for preparing macromonomers maybe also be used for preparing the polymacromonomers. A supercriticalprocess can also be used, preferably a supercritical process above themelting point of the macromonomers being produced is used, preferably asupercritical process above the cloud point of the polymerization systemis used. For more information on the details of the supercriticalprocess (including definitions of cloud point and polymerization system)please see WO 2004/026921.

In an alternate embodiment, other additives may be used, such as diethylzinc, in combination with the catalyst compounds (preferably more thanone, such as two) and activators.

This invention further relates to a process, preferably an in-lineprocess, preferably a continuous process, to produce polymacromonomer,comprising introducing monomer and catalyst system into a reactor,obtaining a reactor effluent containing macromonomer, removing unusedmonomer and/or other volatiles, optionally removing (such as flashingoff) solvent, obtaining macromonomer (such as those described herein)essentially free of residual monomer, introducing macromonomer andcatalyst system into a reaction zone (such as a reactor, an extruder, apipe and/or a pump) and obtaining polymacromonomer (such as thosedescribed herein).

This invention also relates to a two stage process to obtainpolymacromonomer comprising contacting olefin monomer with a catalystsystem, obtaining macromonomer and thereafter contacting themacromonomer with a catalyst system and thereafter obtainingpolymacromonomer.

In a preferred embodiment, the temperature of the polymerization may befrom 60 to 150° C., preferably 70 to 140° C., preferably 80 to 130° C.

In a preferred embodiment, the reaction time of the polymerization isfrom 1 minute to 9 hours, preferably 10 min to 3 hours, preferably 20min to 2 hours, preferably 30 to 90 min, alternately 5 min to 3 hours,alternately 10 min to 2 hours, alternately 15 min to 90 min.

In a preferred embodiment the reactor contains less than 90 wt % diluentor solvent, preferably less than 85 wt %, preferably less than 80 wt %,based upon the weight of the solvent and monomers entering the reactor.

In a preferred embodiment the weight ratio of macromonomer to catalystcompound (including activator) entering the reactor is 10:1 to 20,000:1,preferably 100:1 to 15000:1, preferably 500:1 to 10000:1, preferably50:1 to 15000:1, preferably 100:1 to 10000:1.

In a preferred embodiment, the comonomer contains only, or consistsessentially of or consists of, C₂ to C₁₈ (alternately C₂ to C₁₂) linearalpha olefin monomer units (preferably ethylene, propylene, butene,octene, decene, or dodecene, preferably ethylene and propylene). Inanother embodiment the comonomer does not comprise any styrenic monomer.In another embodiment the comonomer does not comprise any cyclicmonomer. In another embodiment the macromonomer does not comprise anyaromatic containing monomer (also called aromatic monomer units). Inanother embodiment the comonomer comprises 1 wt % or less of a styrenicmonomer, a cyclic monomer or an aromatic containing monomer, preferablyless than 0.5 wt %, preferably 0 wt %, based upon the weight of thecomonomer entering the reaction zone.

In a preferred embodiment the polymacromonomer comprises at least 15 wt% propylene, alternately at least 20% propylene, alternately at least50% propylene, alternately 100 wt % propylene (with the balance beingmade up of one or more of ethylene and or C₄ to C₁₂ olefin monomers(preferably linear alpha olefin monomers, preferably ethylene, butene,hexene, and octene).

In a preferred embodiment the polymacromonomer comprises at least 70 wt% ethylene, alternately at least 80% ethylene, alternately at least 90%ethylene, alternately 100 wt % ethylene (with the balance being made upof one or more of C₃ to C₁₂ olefin monomers (preferably linear alphaolefin monomers, preferably propylene, buthene, hexene, and octene).

In another embodiment the macromonomer can be copolymerized with analpha-omega diene, such as 1,5-hexadiene, 1,7-octadiene, or a cyclicdiene such as norbornadiene or cyclopentadiene.

In a preferred embodiment, the polymacromonomers can be produced usingone or more activators (including all activators described above) incombination with one or more catalyst compounds capable of polymerizingvinyl terminated macromonomers. A catalyst compound or catalyst systemis determined to be capable of polymerizing vinyl terminatedmacromonomers by taking the catalyst compound (plus an activator) or thecatalyst system in question and combining it with 1-octene at thereactor conditions in question (such as 80° C.). If the catalystcompound or catalyst system can polymerize 1-octene to a number averagemolecular weight of 1000 or more, then the catalyst system can performin the instant invention.

Catalysts useful to polymerize the macromonomers include those describedin U.S. Pat. No. 7,126,031, especially the compound represented by theformula:

Other useful catalysts include dimethylsilyl(cyclopentadienyl)(cyclododecylamido) titanium dimethyl,dibenzylmethyl(cyclopentadienyl)(fluorenyl)hafnium dimethyl,dimethylgermanium bisindenyl hafnium dimethyl,diphenylmethyl(cyclopentadienyl)(fluorenyl)hafnium dimethyl.

Further useful catalysts include the racemic versions of: dimethylsilyl(2-methyl-4-phenylindenyl)zirconium dichloride, dimethylsilyl(2-methyl-4-phenylindenyl) zirconium dimethyl, dimethylsilyl(2-methyl-4-phenylindenyl)hafnium dichloride, dimethylsilyl(2-methyl-4-phenylindenyl) hafnium dimethyl, dimethylsilylbis(indenyl)hafnium dimethyl, dimethylsilyl bis(indenyl)hafniumdichloride, dimethylsilyl bis(indenyl)zirconium dimethyl, dimethylsilylbis(indenyl)zirconium dichloride.

Further useful catalysts include the racemic isomers of:dimethylsilanediylbis(2-methylindenyl)metal dichloride;dimethylsilanediylbis(indenyl)metal dichloride;dimethylsilanediylbis(indenyl)metal dimethyl;dimethylsilanediylbis(tetrahydroindenyl)metal dichloride;dimethylsilanediylbis(tetrahydroindenyl)metal dimethyl;dimethylsilanediylbis(indenyl)metal diethyl; anddibenzylsilanediylbis(indenyl)metal dimethyl; wherein the metal ischosen from Zr, Hf, or Ti.

Preferred activators for use with the above catalyst compounds include:dimethylaniliniumtetrakis(pentafluorophenyl) borate,N,N-dimethylanilinium tetra(perfluorophenyl)borate, triphenylcarboniumperfluorotetraphenylborate, dimethylaniliniumperfluorotetranaphthylborate, 4-tert-butylaniliniumbis(pentafluorophenyl)bis(perfluoro-2-napthyl)borate,4-tert-butylanilinium(pentafluorophenyl)tris(perfluoro-2-napthyl)borate, dimethylaniliniumtetrakis(perfluoro-2-napthyl)borate, dimethylaniliniumtetrakis(3,5(pentafluorophenyl)perfluorophenylborate); andtris-perfluorophenyl boron.

Additional activators useful in combination with the catalyst compoundsdescribed above to make the polymacromonomers include those describedabove for use in making the macromonomers. Likewise the processes forproducing the polymacromonomers may generally be used to produce thepolymacromonomers.

Polymacromonomer

In a preferred embodiment, the degree of polymerization for thepolymacromonomer is 3 or more, alternately 5 or more, alternately 6 ormore, alternately 10 or more, alternately 100 or more, alternately 150or more, alternately 200 or more.

In another embodiment, at least 70% of the macromonomer is consumed inthe polymerization, preferably at least 75%, preferably at least 80%,preferably at least 85%, preferably at least 90%, preferably at least95%, preferably at least 98%, as determined by ¹H NMR described in theExperimental section below.

In a preferred embodiment, the polymacromonomer has:

a) a g value of less than 0.5 (preferably less than 0.4, preferably lessthan 0.3, preferably less than 0.25),

b) an Mw of greater than 20,000 g/mol (preferably 30,000 to 1,000,000,preferably 40,000 to 700,000),

c) an Mn of greater than 8,000 g/mol (preferably 15,000 to 400,000,preferably 30,000 to 200,000),

d) a branching index (g′_(vis)) of less than 0.5 (preferably less than0.4, preferably less than 0.3, preferably less than 0.2, preferably lessthan 0.1, preferably less than 0.05), and

e) a melting point of 50° C. or more, preferably 60° C. or more,preferably 70° C. or more, preferably 80° C. or more, preferably 90° C.or more, preferably 100° C. or more, preferably 120° C. or more,preferably from 50 to 200° C., or alternately an Hm of 20 J/g or less,preferably 15 J/g or less.

In another embodiment, the polymacromonomer contains less than 1000 ppmof a group 4 metal (preferably less than 750 ppm or Ti, Hf and/or Zr,preferably less than 500 ppm). Alternately, the polymacromonomercontains less than 1000 ppm of lithium (preferably less than 750 ppm oflithium, preferably less than 500 ppm of lithium).

In a preferred embodiment, the polymacromonomer comprises less than 3 wt% of functional groups selected from hydroxide, aryls and substitutedaryls, halogens, alkoxys, carboxylates, esters, acrylates, oxygen,nitrogen, and carboxyl, preferably less than 2 wt %, more preferablyless than 1 wt %, more preferably less than 0.5 wt %, more preferablyless than 0.1 wt %, more preferably 0 wt %, based upon the weight of thepolymacromonomer.

In another preferred embodiment, the polymacromonomer is amorphous,isotactic or syndiotactic, preferably isotactic. In another embodiment,the polymacromonomer is a propylene homopolymer or propylenehomo-oligomer that may be amorphous, isotactic or syndiotactic,preferably isotactic. In another embodiment, the polymacromonomer is apropylene copolymer or propylene co-oligimer that may be amorphous,isotactic or syndiotactic, preferably isotactic.

In another embodiment the macromonomer comprises less than 30 wt %amorphous material, preferably less than 20 wt %, preferably less than10 wt %, preferably less than 5 wt %.

In another embodiment, any polymacromonomer described herein may have aheat of fusion of 60 J/g or more, preferably 70 J/g or more, preferably90 J/g or more, preferably 120 J/g or more, preferably 160 J/g or moreor 15 J/g or less. In a preferred embodiment, the polymacromonomercomprises two or more different macromonomers, preferably three or moredifferent macromonomers, preferably four or more differentmacromonomers. By different macromonomers is meant that themacromonomers differ in composition (such as monomer content orcomonomer distribution within the macromonomer) or molecular weight. Forexample, in an embodiment, the polymacromonomer can comprise a propylenemacromonomer and an ethylene macromonomer, or a propylene macromonomerand an ethylene-propylene macromonomer, or an ethylene macromonomer andan propylene-ethylene macromonomer. In a particularly preferredembodiment, the entire spectrum from 100% polyethylene macromonomer to100% polypropylene macromonomer with propylene rich and ethylene richvariations in between is available, including amorphous and crystallinevariations. Table 1 below sets out some particularly preferredcombinations of macromonomers, where Vinyl-PE is a ethylenemacromonomer, preferably having crystalline structure (e.g. a Tm of 60°C. or more) and 0 to 10 wt % comonomer, and any of the propertiesdescribed above, Vinyl-aPP is a propylene macromonomer with an amorphouscontent of at least 10% (preferably at least 50%, preferably at least95%) and preferably having from 0 to 10 wt % comonomer, Vinyl iPP is apropylene macromonomer with an isotactic pentad content of at least 50%and preferably having from 0 to 10 wt % comonomer and/or a melting pointof at least 70° C., Vinyl-EP is an ethylene-propylene macromonomerhaving 10 to 50 wt % propylene and 90 to 50 wt % ethylene. Vinyl-PS is astyrene macromonomer, having from 0 to 50 wt % comonomer. Vinyl-pe is ais an propylene-ethylene macromonomer having 10 to 50 wt % ethylene and90 to 50 wt % propylene. Where the macromonomers have the same name inthe table, please consider that they differ in another means, such asmolecular weight or crystallinity.

Macro- Vinyl- Vinyl- Vinyl- Vinyl- monomer Vinyl-PE aPP iPP EP PSVinyl-pe Vinyl-PE X X X X X X Vinyl-aPP X X X X X X Vinyl-iPP X X X X XX Vinyl-EP X X X X X X Vinyl-PS X X X X X X Vinyl-pe X X X X X X

In a preferred embodiment, the polymacromonomer comprises at least twomacromonomers where the first macromonomer comprises 60 wt % or more ofethylene and the second macromonomer comprises 60 wt % or more ofpropylene.

In another embodiment, a termacromonomer is present to produce apolymacromonomer having three different macromonomers, such asVinyl-aPP+Vinyl-PE+vinyl-EP.

Alternately, the polymacromonomer can comprise macromonomers that differin molecular weight (Mw) by at least 200 g/mol, alternately by at least300 g/mol, alternately by at least 1000 g/mol, alternately by at least3000 g/mol, alternately by at least 5000 g/mol. In another embodiment,at least 50 wt % (preferably at least 60 wt %, preferably at least 70 wt%, preferably at least 80 wt %) of the monomers in the macromonomersdiffer by in molecular weight (Mw) by at least 200 g/mol, alternately byat least 300 g/mol, alternately by at least 1000 g/mol, alternately byat least 3000 g/mol, alternately by at least 5000 g/mol.

Alternately, the polymacromonomer can comprise macromonomers that differin monomer content where the monomers differ by at least one carbon,alternately by at least 2 carbons, alternately by at least 4 carbons,alternately by at least 6 carbons. In another embodiment, at least 50 wt% (preferably at least 60 wt %, preferably at least 70 wt %, preferablyat least 80 wt %) of the monomers in the macromonomers differ by atleast one carbon, alternately by at least 2 carbons, alternately by atleast 4 carbons, alternately by at least 6 carbons.

Alternately, the polymacromonomer can comprise macromonomers that differin total comonomer content by at least 2 wt %, preferably by at least 5wt %, preferably by at least 10 wt %, preferably by at least 15 wt %,preferably by at least 20 wt %.

In another embodiment, the polymacromonomer comprises at least twodifferent macromonomers where one macromonomer has a Tm of 60° C. ormore (preferably 70° C. or more, preferably 80° C. or more, preferably90° C. or more, preferably 100° C. or more, preferably 110° C. or more,preferably 120° C. or more, preferably 130° C. or more) and the secondmonomer has an Hm of 20 J/g or less, preferably 15 J/g or less.Preferably both monomers also have: 1) from 20 to 600 carbon atoms; 2)an Mn of 280 g/mol or more; 3) an Mw of 400 g/mol or more; 4) an Mz of600 g/mol or more; 5) an Mw/Mn of 1.5 or more; 6) at least 70% vinyltermination (relative to total unsaturation); and 7) less than 5 wt %aromatic containing monomer. Preferably the first and secondmacromonomers are ethylene based (preferably each macromonomer comprisesat least 50 wt % ethylene, preferably at least 60 wt %).

In additional embodiments, one could manipulate the polymerizationconditions such that blocks of macromonomers can be made (e.g. pulsingin different macromonomers at certain time intervals). For example,propylene macromonomers could be polymerized then a large amount ofethylene macromonomer could be polymerized to create a diblockpolymacromonomer, or a mixture of polymacromonomers could be made.

In another embodiment this invention relates to:

-   1. A polymacromonomer comprising at least one macromonomer and from    0 to 20 wt % of a C₂ to C₁₈ comonomer, wherein the macromonomer has:

1) from 20 to 800 carbon atoms,

2) an Mn of 280 g/mol or more,

3) an Mw of 400 g/mol or more,

4) an Mz of 600 g/mol or more,

5) an Mw/Mn of 1.5 or more,

6) vinyl termination of at least 70% (as determined by ¹H NMR) relativeto total unsaturations,

7) a melting point (Tm) of 60° C. or more or an Hm of 20 J/g or less,and

8) less than l 0 wt % aromatic containing monomer, based upon the weightof the macromonomer; and

wherein the polymacromonomer has:

a) a g value of less than 0.6,

b) an Mw of greater than 30,000 g/mol,

c) an Mn of greater than 20,000 g/mol,

d) a branching index (g′)_(vis) of less than 0.5,

e) a melting point of 50° C. or more or an Hm or 20 J/g or less,

f) less than 25% vinyl terminations (as measured by ¹H NMR) relative tototal unsaturations,

g) at least 70 wt % macromonomer, based upon the weight of thepolymacromonomer, and

h) from 0 to 20 wt % aromatic containing monomer, based upon the weightof the polymacromonomer.

-   2. The polymacromonomer of paragraph 1 wherein the polymacromonomer    contains 0 wt % aromatic containing monomer.-   3. The polymacromonomer of paragraph 1 or 2 wherein the    polymacromonomer contains 0 wt % styrenic monomer.-   4. The polymacromonomer of paragraph 1, 2 or 3 wherein the    macromonomer is isotactic.-   5. The polymacromonomer of paragraph 1, 2, 3, or 4 wherein the    polymacromonomer comprises at least 70 wt % macromonomer comprising    at least 50 wt % propylene.-   6. The polymacromonomer of claim 1, 2, 3, 4, or 5 wherein the    polymacromonomer comprises at least 70 wt % macromonomer comprising    at least 50 wt % ethylene.-   7. The polymacromonomer of any of paragraphs 1 to 6 wherein the    polymacromonomer comprises two or more different macromonomers.-   8. The polymacromonomer of paragraph 7 wherein the macromonomers    differ in molecular weight (Mw) by at least 200 g/mol.-   9. The polymacromonomer of paragraph 7 or 8 wherein the first    macromonomer has a melting point of 60° C. or more and the second    macromonomer has an Hm of 20 J/g or less.-   10. The polymacromonomer of any of paragraphs 1 to 10 wherein the    macromonomer comprises a propylene polymer having a g′_(vis) of 0.95    or less.-   11. The polymacromonomer of any of paragraphs 1 to 11 wherein the    macromonomer comprises a copolymer of 65 to 80 wt % ethylene and 20    to 35 wt % propylene (based upon the weight of the copolymer) and    has a Hm of 15 J/g or less.-   12. A polymacromonomer comprising at least one macromonomer and from    0 to 20 wt % of a C₂ to C₁₈ comonomer, wherein the polymacromonomer    has:

a) a g value of less than 0.6,

b) an Mw of greater than 30,000 g/mol,

c) an Mn of greater than 20,000 g/mol,

d) a branching index (g′)_(vis) of less than 0.5,

e) less than 25% vinyl terminations (as measured by ¹H NMR) relative tototal unsaturations,

f) at least 70 wt % macromonomer, based upon the weight of thepolymacromonomer, and

g) from 0 to 20 wt % aromatic containing monomer, based upon the weightof the polymacromonomer; and the macromonomer comprises one or more of:

i) propylene co-oligomer having an Mn of 300 to 30,000 g/mol comprising10 to 90 mol % propylene and 10 to 90 mol % of ethylene, wherein theoligomer has at least X % allyl chain ends (relative to totalunsaturations), where: 1) X=(−0.94 (mol % ethylene incorporated)+100),when 10 to 60 mol % ethylene is present in the co-oligomer, and 2) X=45,when greater than 60 and less than 70 mol % ethylene is present in theco-oligomer, and 3) X=(1.83*(mol % ethylene incorporated)−83), when 70to 90 mol % ethylene is present in the co-oligomer; and/or

ii) propylene oligomer, comprising more than 90 mol % propylene and lessthan 10 mol % ethylene, wherein the oligomer has: at least 93% allylchain ends, an Mn of about 500 to about 20,000 g/mol, an isobutyl chainend to allylic vinyl group ratio of 0.8:1 to 1.35:1.0, and less than1400 ppm aluminum; and/or

iii) propylene oligomer, comprising at least 50 mol % propylene and from10 to 50 mol % ethylene, wherein the oligomer has: at least 90% allylchain ends, Mn of about 150 to about 10,000 g/mol, and an isobutyl chainend to allylic vinyl group ratio of 0.8:1 to 1.3:1.0, wherein monomershaving four or more carbon atoms are present at from 0 to 3 mol %;and/or

iv) propylene oligomer, comprising at least 50 mol % propylene, from 0.1to 45 mol % ethylene, and from 0.1 to 5 mol % C4 to C12 olefin, whereinthe oligomer has: at least 87% allyl chain ends (alternately at least90%), an Mn of about 150 to about 10,000 g/mol, and an isobutyl chainend to allylic vinyl group ratio of 0.8:1 to 1.35:1.0; and/or

v) propylene oligomer, comprising at least 50 mol % propylene, from 0.1to 45 wt % ethylene, and from 0.1 to 5 mol % diene, wherein the oligomerhas: at least 90% allyl chain ends, an Mn of about 150 to about 10,000g/mol, and an isobutyl chain end to allylic vinyl group ratio of 0.7:1to 1.35:1.0; and/or

vi) a homooligomer, comprising propylene, wherein the oligomer has: atleast 93% allyl chain ends, an Mn of about 500 to about 20,000 g/mol, anisobutyl chain end to allylic vinyl group ratio of 0.8:1 to 1.2:1.0, andless than 1400 ppm aluminum.

-   13. The polymacromonomer of paragraph 12 wherein the macromonomer is    a propylene co-oligomer having an Mn of 300 to 30,000 g/mol    comprising 10 to 90 mol % propylene and 10 to 90 mol % of ethylene,    wherein the oligomer has at least X % allyl chain ends (relative to    total unsaturations), where: 1) X=(−0.94 (mol % ethylene    incorporated)+100), when 10 to 60 mol % ethylene is present in the    co-oligomer, and 2) X=45, when greater than 60 and less than 70 mol    % ethylene is present in the co-oligomer, and 3) X=(1.83*(mol %    ethylene incorporated)−83), when 70 to 90 mol % ethylene is present    in the co-oligomer;-   14. The polymacromonomer of any of paragraphs 1 to 13 wherein the    macromonomers are liquid at 25° C.-   15. A process to produce the polymacromonomers of paragraphs 1 to 14    comprising contacting macromonomer and up to 40 wt % of C₂ to C₁₈    comonomer with a catalyst system capable of polymerizing vinyl    terminated macromonomer, wherein the macromonomer has:

1) from 20 to 800 carbon atoms,

2) an Mn of 280 g/mol or more,

3) an Mw of 400 g/mol or more,

4) an Mz of 600 g/mol or more,

5) an Mw/Mn of 1.5 or more,

6) at least 70% vinyl termination (as measured by ¹H NMR) relative tototal unsaturations,

7) a melting point Tm of 60° C. or more or an Hm of 20 J/g or less, and

8) less than 20 wt % aromatic containing monomer;

under polymerization conditions of a temperature of 60 to 130° C. and areaction time of 1 to 90 minutes, wherein the molar ratio of allcomonomer present in the reactor to all macromonomer present in thereactor is 3:1 or less and where conversion of macromonomer topolymacromonomer is 70 wt % or more; andobtaining a polymacromonomer having:

a) a g value of less than 0.6,

b) an Mw of greater than 30,000 g/mol,

c) an Mn of greater than 20,000 g/mol,

d) a branching index (g′)_(vis) of less than 0.5, and

e) a melting point of 50° C. or more or an Hm of 20 J/g or less,

f) less that 25% vinyl termination (as measured by ¹H NMR) relative tototal unsaturations,

g) at least 70 wt % macromonomer, based upon the weight of thepolymacromonomer, and

h) from 0 to 20 wt % aromatic containing monomer, based upon the weightof the polymacromonomer.

-   16. The process of paragraph 15 wherein the degree of polymerization    of the polymacromer is 6 or more.-   17. The process of paragraph 15 wherein the degree of polymerization    of the polymacromer is 100 or more.-   18. The process of paragraph 15, 16, or 17 wherein the catalyst    system capable of polymerizing vinyl terminated macromonomer    comprises the compound represented by the formula:

-   19. The process of paragraph 15, 16, 17, or 18 wherein the catalyst    system capable of polymerizing vinyl terminated macromonomer    comprise one or more of:

dimethylsilyl (cyclopentadienyl)(cyclododecylamido)titanium dimethyl,dibenzylmethyl(cyclopentadienyl)(fluorenyl)hafnium dimethyl,diphenylmethyl(cyclopentadienyl)(fluorenyl)hafnium dimethyl,dimethylgermanium bisindenyl hafnium dimethyl,rac-dimethylsilyl(2-methyl-4-phenylindenyl) zirconium dichloride,rac-dimethylsilyl(2-methyl-4-phenylindenyl)zirconium dimethyl,rac-dimethylsilyl(2-methyl-4-phenylindenyl) hafnium dichloride,rac-dimethylsilyl(2-methyl-4-phenylindenyl)hafnium dimethyl,rac-dimethylsilyl bis(indenyl)hafnium dimethyl, rac-dimethylsilylbis(indenyl)hafnium dichloride, rac-dimethylsilyl bis(indenyl)ziconiumdimethyl, rac-dimethylsilyl bis(indenyl)zirconium dichlorider,ac-dimethylsilanediylbis(2-methylindenyl)metal dichloride;rac-dimethylsilanediylbis(indenyl)metal dichloride;rac-dimethylsilanediylbis(indenyl)metal dimethyl;rac-dimethylsilanediylbis(tetrahydroindenyl)metal dichloride;rac-dimethylsilanediylbis(tetrahydroindenyl)metal dimethyl;rac-dimethylsilanediylbis(indenyl)metal diethyl; andrac-dibenzylsilanediylbis(indenyl)metal dimethyl; wherein the metal ischosen from Zr, Hf, or Ti.

-   20. The process of claim any of paragraphs 15 to 19 wherein the    catalyst system capable of polymerizing vinyl terminated    macromonomer comprises one or more of:    dimethylaniliniumtetrakis(pentafluorophenyl) borate,    N,N-dimethylanilinium tetra(perfluorophenyl)borate,    triphenylcarbonium perfluorotetraphenylborate, dimethylanilinium    perfluorotetranaphthylborate, 4-tert-butylanilinium    bis(pentafluorophenyl)bis(perfluoro-2-napthyl)borate,    4-tert-butylanilinium    (pentafluorophenyl)tris(perfluoro-2-napthyl)borate,    dimethylanilinium tetrakis(perfluoro-2-napthyl)borate,    dimethylanilinium    tetrakis(3,5(pentafluorophenyl)perfluorophenylborate); and    tris-perfluorophenyl boron.-   21. The process of any of paragraphs 15 to 20 further comprising    preparing the macromonomer by contacting monomer with a catalyst    system comprising activator and catalyst represented by the formula:

or rac-Me₂Si-bis(2-R-indenyl)MX₂ or rac-Me₂Si-bis(2-R,4-Ph-indenyl)MX₂,

-   where R is an alkyl group, Ph is phenyl or substituted phenyl, M is    Hf, Zr or Ti, and X is a halogen or alkyl group.-   22. A process to produce polymacromonomers comprising contacting    macromonomer and up to 40 wt % of C₂ to C₁₈ comonomer with a    catalyst system capable of polymerizing vinyl terminated    macromonomer, wherein the macromonomer is produced by homogenous    process for making the propylene co-oligomer of paragraph 12 or 13,    said process having productivity of at least 4.5×10³ g/mmol/hr,    wherein the process comprises:-   contacting, at a temperature of from 35° C. to 150° C., propylene,    0.1 to 70 mol % ethylene and from 0 to about 5 wt % hydrogen in the    presence of a catalyst system comprising an activator and at least    one metallocene compound represented by the formula I, II, III, or    IV above: where Hf is hafnium;-   each X is, independently, selected from the group consisting of    hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides,    amides, alkoxides, sulfides, phosphides, halogens, dienes, amines,    phosphines, ethers, or a combination thereof, preferably methyl,    ethyl, propyl, butyl, phenyl, benzyl, chloride, bromide, iodide,    (alternately two X's may form a part of a fused ring or a ring    system);-   each Q is, independently carbon or a heteroatom, preferably C, N, P,    S (preferably at least one Q is a heteroatom, alternately at least    two Q's are the same or different heteroatoms, alternately at least    three Q's are the same or different heteroatoms, alternately at    least four Q's are the same or different heteroatoms);-   each R¹ is, independently, a C₁ to C₈ alkyl group, preferably a C₁    to C₈ linear alkyl group, preferably methyl ethyl, propyl, butyl,    pentyl, hexyl, heptyl or octyl, R¹ may the same or different as R²;-   each R² is, independently, a C₁ to C₈ alkyl group, preferably a C₁    to C₈ linear alkyl group, preferably methyl ethyl, propyl, butyl,    pentyl, hexyl, heptyl or octyl, preferably R¹ and/or R² are not    branched;-   each R³ is, independently, hydrogen, or a substituted or    unsubstituted hydrocarbyl group having from 1 to 8 carbon atoms,    preferably 1 to 6 carbon atoms, preferably a substituted or    unsubstituted C₁ to C₈ linear alkyl group, preferably methyl ethyl,    propyl, butyl, pentyl, hexyl, heptyl, octyl, provided however that    at least three R³ groups are not hydrogen (alternately four R³    groups are not hydrogen, alternately five R³ groups are not    hydrogen);-   each R⁴ is, independently, hydrogen or a substituted or    unsubstituted hydrocarbyl group, a heteroatom or heteroatom    containing group, preferably a substituted or unsubstituted    hydrocarbyl group having from 1 to 20 carbon atoms, preferably 1 to    8 carbon atoms, preferably a substituted or unsubstituted C₁ to C₈    linear alkyl group, preferably methyl ethyl, propyl, butyl, pentyl,    hexyl, heptyl, octyl, substituted phenyl (such as propyl phenyl),    phenyl, silyl, substituted silyl, (such as CH₂SiR′, where R′ is a C₁    to C₁₂ hydrocarbyl, such as methyl, ethyl, propyl, butyl, phenyl);-   R⁵ is hydrogen or a C₁ to C₈ alkyl group, preferably a C₁ to C₈    linear alkyl group, preferably methyl, ethyl, propyl, butyl, pentyl,    hexyl, heptyl or octyl;-   R⁶ is hydrogen or a C₁ to C₈ alkyl group, preferably a C₁ to C₈    linear alkyl group, preferably methyl, ethyl, propyl, butyl, pentyl,    hexyl, heptyl or octyl;-   each R⁷ is, independently, hydrogen, or a C₁ to C₈ alkyl group,    preferably a C₁ to C₈ linear alkyl group, preferably methyl ethyl,    propyl, butyl, pentyl, hexyl, heptyl or octyl, provided however that    at least seven R⁷ groups are not hydrogen, alternately at least    eight R⁷ groups are not hydrogen, alternately all R⁷ groups are not    hydrogen, (preferably the R⁷ groups at the 3 and 4 positions on each    Cp ring of Formula IV are not hydrogen);-   N is nitrogen;-   T is a bridge, preferably, Si or Ge, preferably Si;-   each R^(a), is independently, hydrogen, halogen or a C₁ to C₂₀    hydrocarbyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl,    heptyl, octyl, phenyl, benzyl, substituted phenyl, and two R^(a) can    form a cyclic structure including aromatic, partially saturated, or    saturated cyclic or fused ring system;    and further provided that any two adjacent R groups may form a fused    ring or multicenter fused ring system where the rings may be    aromatic, partially saturated or saturated.-   23. A process to produce polymacromonomers comprising contacting    macromonomer and up to 40 wt % of C₂ to C₁₈ comonomer with a    catalyst system capable of polymerizing vinyl terminated    macromonomer, wherein the macromonomer is produced by a homogenous    process for making the propylene homo-oligomer of paragraph 12 or    13, said process having a productivity of at least 4.5×10⁶    g/mol/min, wherein the process comprises:-   contacting, at a temperature of from 30° C. to 120° C., propylene, 0    mol % comonomer and from 0 to about 5 wt % hydrogen in the presence    of a catalyst system comprising an activator and at least one    metallocene compound represented by the formula I, II, III, or IV    above: where Hf is hafnium;-   each X is, independently, selected from the group consisting of    hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides,    amides, alkoxides, sulfides, phosphides, halogens, dienes, amines,    phosphines, ethers, or a combination thereof, preferably methyl,    ethyl, propyl, butyl, phenyl, benzyl, chloride, bromide, iodide,    (alternately two X's may form a part of a fused ring or a ring    system);-   each Q is, independently carbon or a heteroatom, preferably C, N, P,    S (preferably at least one Q is a heteroatom, alternately at least    two Q's are the same or different heteroatoms, alternately at least    three Q's are the same or different heteroatoms, alternately at    least four Q's are the same or different heteroatoms);-   each R¹ is, independently, a C₁ to C₈ alkyl group, preferably a C₁    to C₈ linear alkyl group, preferably methyl ethyl, propyl, butyl,    pentyl, hexyl, heptyl or octyl, R¹ may the same or different as R²;-   each R² is, independently, a C₁ to C₈ alkyl group, preferably a C₁    to C₈ linear alkyl group, preferably methyl ethyl, propyl, butyl,    pentyl, hexyl, heptyl or octyl, preferably R¹ and/or R² are not    branched;-   each R³ is, independently, hydrogen, or a substituted or    unsubstituted hydrocarbyl group having from 1 to 8 carbon atoms,    preferably 1 to 6 carbon atoms, preferably a substituted or    unsubstituted C₁ to C₈ linear alkyl group, preferably methyl ethyl,    propyl, butyl, pentyl, hexyl, heptyl, octyl, provided however    that: 1) all five R³ groups are methyl, or 2) four R³ groups are not    hydrogen and at least one R³ group is a C₂ to C₈ substituted or    unsubstituted hydrocarbyl (preferably at least two, three, four or    five R³ groups are a C₂ to C₈ substituted or unsubstituted    hydrocarbyl);-   each R⁴ is, independently, hydrogen or a substituted or    unsubstituted hydrocarbyl group, a heteroatom or heteroatom    containing group, preferably a substituted or unsubstituted    hydrocarbyl group having from 1 to 20 carbon atoms, preferably 1 to    8 carbon atoms, preferably a substituted or unsubstituted C₁ to C₈    linear alkyl group, preferably methyl ethyl, propyl, butyl, pentyl,    hexyl, heptyl, octyl, substituted phenyl (such as propyl phenyl),    phenyl, silyl, substituted silyl, (such as CH₂SiR′, where R′ is a C₁    to C₁₂ hydrocarbyl, such as methyl, ethyl, propyl, butyl, phenyl);-   R⁵ is hydrogen or a C₁ to C₈ alkyl group, preferably a C₁ to C₈    linear alkyl group, preferably methyl, ethyl, propyl, butyl, pentyl,    hexyl, heptyl or octyl;-   R⁶ is hydrogen or a C₁ to C₈ alkyl group, preferably a C₁ to C₈    linear alkyl group, preferably methyl, ethyl, propyl, butyl, pentyl,    hexyl, heptyl or octyl;-   each R⁷ is, independently, hydrogen, or a C₁ to C₈ alkyl group,    preferably a C₁ to C₈ linear alkyl group, preferably methyl ethyl,    propyl, butyl, pentyl, hexyl, heptyl or octyl, provided however that    at least seven R⁷ groups are not hydrogen, alternately at least    eight R⁷ groups are not hydrogen, alternately all R⁷ groups are not    hydrogen, (preferably the R⁷ groups at the 3 and 4 positions on each    Cp ring of Formula IV are not hydrogen);-   N is nitrogen;-   T is a bridge, preferably, Si or Ge, preferably Si;    each R^(a), is independently, hydrogen, halogen or a C1 to C20    hydrocarbyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl,    heptyl, octyl, phenyl, benzyl, substituted phenyl, and two R^(a) can    form a cyclic structure including aromatic, partially saturated, or    saturated cyclic or fused ring system;    and further provided that any two adjacent R groups may form a fused    ring or multicenter fused ring system where the rings may be    aromatic, partially saturated or saturated.

EXPERIMENTAL

All molecular weights are number average in g/mol unless otherwisenoted.

Materials

Catalyst 1 is 1,1′ diphenylmethylene(cyclopentadienyl)(fluorenyl)hafniumdimethyl,

Catalyst 2 is rac-dimethylsilylbis(indenyl)hafnium dimethyl,

Catalyst 3 is rac-dimethylsilylbis(2-methyl 4-phenyl indenyl)hafniumdimethyl,

Catalyst 4 was prepared according to the procedures in U.S. Pat. No.7,126,031. Catalyst 5 was prepared and purified according to theprocedure in G. J. P. Britovsek, V. C. Gibson, S. J. McTavish, G. A.Solan, B. S. Kimberley, P. J. Maddox, A. J. P. White, Williams, Chem.Comm. 1998, 849.

Activator A is N,N-dimethylanilinium tetra (perfluorophenyl)borate.

Activator B is methylalumoxane (30 wt % in toluene) purchased fromAlbemarle.

Characterization

Gel Permeation Chromotography

Mw, Mz number of carbon atoms, g value and g′_(vis) are determined byusing a High Temperature Size Exclusion Chromatograph (either fromWaters Corporation or Polymer Laboratories), equipped with three in-linedetectors, a differential refractive index detector (DRI), a lightscattering (LS) detector, and a viscometer. Experimental details,including detector calibration, are described in: T. Sun, P. Brant, R.R. Chance, and W. W. Graessley, Macromolecules, Volume 34, Number 19,6812-6820, (2001) and references therein. Three Polymer LaboratoriesPLgel 10 mm Mixed-B LS columns are used. The nominal flow rate is 0.5cm³/min, and the nominal injection volume is 300 μL. The varioustransfer lines, columns and differential refractometer (the DRIdetector) are contained in an oven maintained at 145° C. Solvent for theexperiment is prepared by dissolving 6 grams of butylated hydroxytoluene as an antioxidant in 4 liters of Aldrich reagent grade 1, 2, 4trichlorobenzene (TCB). The TCB mixture is then filtered through a 0.7μm glass pre-filter and subsequently through a 0.1 μm Teflon filter. TheTCB is then degassed with an online degasser before entering the SizeExclusion Chromatograph. Polymer solutions are prepared by placing drypolymer in a glass container, adding the desired amount of TCB, thenheating the mixture at 160° C. with continuous agitation for about 2hours. All quantities are measured gravimetrically. The TCB densitiesused to express the polymer concentration in mass/volume units are 1.463g/ml at room temperature and 1.324 g/ml at 145° C. The injectionconcentration is from 0.75 to 2.0 mg/ml, with lower concentrations beingused for higher molecular weight samples. Prior to running each samplethe DRI detector and the injector are purged. Flow rate in the apparatusis then increased to 0.5 ml/minute, and the DRI is allowed to stabilizefor 8 to 9 hours before injecting the first sample. The LS laser isturned on 1 to 1.5 hours before running the samples. The concentration,c, at each point in the chromatogram is calculated from thebaseline-subtracted DRI signal, I_(DRI), using the following equation:C=K _(DRI) I _(DRI)/(dn/dc)where K_(DRI) is a constant determined by calibrating the DRI, and(dn/dc) is the refractive index increment for the system. The refractiveindex, n=1.500 for TCB at 145° C. and μ=690 nm. For purposes of thisinvention and the claims thereto (dn/dc)=0.104 for propylene polymers,0.098 for butene polymers and 0.1 otherwise. Units on parametersthroughout this description of the SEC method are such thatconcentration is expressed in g/cm³, molecular weight is expressed ing/mole, and intrinsic viscosity is expressed in dL/g.

The LS detector is a Wyatt Technology High Temperature mini-DAWN. Themolecular weight, M, at each point in the chromatogram is determined byanalyzing the LS output using the Zimm model for static light scattering(M. B. Huglin, LIGHT SCATTERING FROM POLYMER SOLUTIONS, Academic Press,1971):

$\frac{K_{o}c}{\Delta\;{R(\theta)}} = {\frac{1}{{MP}(\theta)} + {2A_{2}c}}$Here, ΔR(θ) is the measured excess Rayleigh scattering intensity atscattering angle θ, c is the polymer concentration determined from theDRI analysis, A₂ is the second virial coefficient [for purposes of thisinvention, A₂=0.0006 for propylene polymers, 0.0015 for butene polymersand 0.001 otherwise], (dn/dc)=0.104 for propylene polymers, 0.098 forbutene polymers and 0.1 otherwise, P(θ) is the form factor for amonodisperse random coil, and K_(o) is the optical constant for thesystem:

$K_{o} = \frac{4\pi^{2}{n^{2}\left( {{dn}/{dc}} \right)}^{2}}{\lambda^{4}N_{A}}$where N_(A) is Avogadro's number, and (dn/dc) is the refractive indexincrement for the system. The refractive index, n=1.500 for TCB at 145°C. and λ=690 nm.

A high temperature Viscotek Corporation viscometer, which has fourcapillaries arranged in a Wheatstone bridge configuration with twopressure transducers, is used to determine specific viscosity. Onetransducer measures the total pressure drop across the detector, and theother, positioned between the two sides of the bridge, measures adifferential pressure. The specific viscosity, η_(s), for the solutionflowing through the viscometer is calculated from their outputs. Theintrinsic viscosity, [η], at each point in the chromatogram iscalculated from the following equation:η_(s) =c[η]+0.3(c[η])²where c is concentration and was determined from the DRI output.

The branching index (g′_(vis)) is calculated using the output of theSEC-DRI-LS-VIS method as follows. The average intrinsic viscosity,[η]_(avg), of the sample is calculated by:

$\lbrack\eta\rbrack_{avg} = \frac{\sum{c_{i}\lbrack\eta\rbrack}_{i}}{\sum c_{i}}$where the summations are over the chromotographic slices, i, between theintegration limits. The branching index g′_(vis) is defined as:

${g^{\prime}{vis}} = \frac{\lbrack\eta\rbrack_{avg}}{{kM}_{v}^{\alpha}}$where, for purpose of this invention and claims thereto, α=0.695 andk=0.000579 for linear ethylene polymers, α=0.705 k=0.000262 for linearpropylene polymers, and α=0.695 and k=0.000181 for linear butenepolymers. M_(y) is the viscosity-average molecular weight based onmolecular weights determined by LS analysis.

“g” also called a “g value” is defined to be Rg² _(pm)/Rg² _(ls), whereRg_(pm) is the radius of gyration for the polymacromer, Rg² _(ls) is theradius of gyration for the linear standard, and Rg_(ls)=K_(s)M^(0.58)where K_(s) is the power law coefficient (0.023 for linear polyethylene,0.0171 for linear polypropylene, and 0.0145 for linear polybutene), andM is the molecular weight as described above, Rg_(pm)=K_(T)M^(αs). α_(s)is the size coefficient for the polymacromer, K_(T) is the power lawcoefficient for the polymacromer. See Macromolecules, 2001, 34,6812-6820, for guidance on selecting a linear standards having themolecular weight and comonomer content, and determining K coefficientsand α exponents.

¹³C NMR

¹³C NMR data was collected at 120° C. in a 10 mm probe using a Varianspectrometer with a ¹Hydrogen frequency of at least 400 MHz. A 90 degreepulse, an acquisition time adjusted to give a digital resolution between0.1 and 0.12 Hz, at least a 10 second pulse acquisition delay time withcontinuous broadband proton decoupling using swept square wavemodulation without gating was employed during the entire acquisitionperiod. The spectra were acquired using time averaging to provide asignal to noise level adequate to measure the signals of interest.Samples were dissolved in tetrachloroethane-d₂ at concentrations between10 to 15 wt % prior to being inserted into the spectrometer magnet.Prior to data analysis spectra were referenced by setting the chemicalshift of the (—CH₂—)_(n) signal where n>6 to 29.9 ppm. Chain ends forquantization were identified using the signals shown in the table below.N-butyl and n-propyl were not reported due to their low abundance (lessthan 5%) relative to the chain ends shown in the table below.

Chain End ¹³CNMR Chemical Shift P~i-Bu 23-5 to 25.5 and 25.8 to 26.3 ppmE~i-Bu 39.5 to 40.2 ppm P~Vinyl 41.5 to 43 ppm E~Vinyl 33.9 to 34.4 ppm

Polypropylene microstructure is determined by ¹³C—NMR spectroscopy,including the concentration of isotactic and syndiotactic diads ([m] and[r]), triads ([mm] and [rr]), and pentads ([mmmm] and [rrrr]). Thedesignation “m” or “r” describes the stereochemistry of pairs ofcontiguous propylene groups, “m” referring to meso and “r” to racemic.Samples are dissolved in d₂-1,1,2,2-tetrachloroethane, and spectrarecorded at 125° C. using a 100 MHz (or higher) NMR spectrometer.Polymer resonance peaks are referenced to mmmm=21.8 ppm. Calculationsinvolved in the characterization of polymers by NMR are described by F.A. Bovey in POLYMER CONFORMATION AND CONFIGURATION (Academic Press, NewYork 1969) and J. Randall in POLYMER SEQUENCE DETERMINATION, ¹³C—NMRMETHOD (Academic Press, New York, 1977).

The “propylene tacticity index”, expressed herein as [m/r], iscalculated as defined in H. N. Cheng, Macromolecules, 17, 1950 (1984).When [m/r] is 0 to less than 1.0, the polymer is generally described assyndiotactic, when [m/r] is 1.0 the polymer is atactic, and when [m/r]is greater than 1.0 the polymer is generally described as isotactic.

The “mm triad tacticity index” of a polymer is a measure of the relativeisotacticity of a sequence of three adjacent propylene units connectedin a head-to-tail configuration. More specifically, in the presentinvention, the mm triad tacticity index (also referred to as the “mmFraction”) of a polypropylene homopolymer or copolymer is expressed asthe ratio of the number of units of meso tacticity to all of thepropylene triads in the copolymer:

${{mm}\mspace{14mu}{Fraction}}\; = \frac{{PPP}({mm})}{{{PPP}({mm})} + {{PPP}({mr})} + {{PPP}({rr})}}$where PPP(mm), PPP(mr) and PPP(rr) denote peak areas derived from themethyl groups of the second units in the possible triad configurationsfor three head-to-tail propylene units, shown below in Fischerprojection diagrams:

The calculation of the mm Fraction of a propylene polymer is describedin U.S. Pat. No. 5,504,172 (homopolymer: column 25, line 49 to column27, line 26; copolymer: column 28, line 38 to column 29, line 67). Forfurther information on how the mm triad tacticity can be determined froma ¹³C-NMR spectrum, see 1) J. A. Ewen, CATALYTIC POLYMERIZATION OFOLEFINS: PROCEEDINGS OF THE INTERNATIONAL SYMPOSIUM ON FUTURE ASPECTS OFOLEFIN POLYMERIZATION, T. Keii and K. Soga, Eds. (Elsevier, 1986), pp.271-292; and 2) U.S. Patent Application US2004/054086 (paragraphs [0043]to [0054]).¹H NMR

¹H NMR data was collected at either room temperature or 120° C. (forpurposes of the claims, 120° C. shall be used) in a 5 mm probe using aVarian spectrometer with a ¹Hydrogen frequency of at least 400 MHz. Datawas recorded using a maximum pulse width of 45°, 8 seconds betweenpulses and signal averaging 120 transients. Spectral signals wereintegrated and the number of unsaturation types per 1000 carbons wascalculated by multiplying the different groups by 1000 and dividing theresult by the total number of carbons.

The ¹HNMR chemical shift regions for the olefin types are defined to bebetween the following spectral regions.

Unsaturation Type Region (ppm) Number of hydrogens per structure Vinyl4.95-5.10 2 Vinylidene 4.70-4.84 2 Vinylene 5.31-5.55 2 Trisubstituted5.11-5.30 1Differential Scanning Calorimetry (DSC)

Crystallization temperature (T_(c)), melting temperature (or meltingpoint, T_(m)), glass transition temperature (T_(g)) and heat of fusion(H_(f)) are measured using Differential Scanning calorimetry (DSC) on acommercially available instrument (e.g., TA Instruments 2920 DSC).Typically, 6 to 10 mg of molded polymer or plasticized polymer aresealed in an aluminum pan and loaded into the instrument at roomtemperature. Data are acquired by heating the sample to at least 30° C.above its melting temperature, typically 220° C. for polypropylene, at aheating rate of 10° C./min. The sample is held for at least 5 minutes atthis temperature to destroy its thermal history. Then the sample iscooled from the melt to at least 50° C. below the crystallizationtemperature, typically −100° C. for polypropylene, at a cooling rate of20° C./min. The sample is held at this temperature for at least 5minutes, and finally heated at 10° C./min to acquire additional meltingdata (second heat). The endothermic melting transition (first and secondheat) and exothermic crystallization transition are analyzed accordingto standard procedures. The melting temperatures (Tm) reported are thepeak melting temperatures from the second heat unless otherwisespecified. For polymers displaying multiple peaks, the meltingtemperature is defined to be the peak melting temperature from themelting trace associated with the largest endothermic calorimetricresponse (as opposed to the peak occurring at the highest temperature).Likewise, the crystallization temperature is defined to be the peakcrystallization temperature from the crystallization trace associatedwith the largest exothermic calorimetric response (as opposed to thepeak occurring at the highest temperature).

Areas under the DSC curve are used to determine the heat of transition(heat of fusion, H_(f), upon melting or heat of crystallization, H_(c),upon crystallization), which can be used to calculate the degree ofcrystallinity (also called the percent crystallinity). The percentcrystallinity (X %) is calculated using the formula: [area under thecurve (in J/g)/H° (in J/g)]*100, where H° is the ideal heat of fusionfor a perfect crystal of the homopolymer of the major monomer component.These values for H° are to be obtained from the Polymer Handbook, FourthEdition, published by John Wiley and Sons, New York 1999, except that avalue of 290 J/g is used for H° (polyethylene), a value of 140 J/g isused for H° (polybutene), and a value of 207 J/g is used for H°(polypropylene).

Heat of melting (Hm) is determined using the DSC procedure above exceptthat the sample is cooled to −100° C., held for 5 minutes then heated at10° C./min to 200° C. Hm is measured on the first melt, no the secondmelt. The Hm sample must have been aged at least 48 hours at roomtemperature and should not be heated to destroy thermal history.

Ethylene Content

Ethylene content in ethylene copolymers is determined by ASTM D 5017-96,except that the minimum signal-to-noise should be 10,000:1. Propylenecontent in propylene copolymers is determined by following the approachof Method 1 in Di Martino and Kelchermans, J. Appl. Polym. Sci. 56, 1781(1995), and using peak assignments from Zhang, Polymer 45, 2651 (2004)for higher olefin comonomers.

Example 1

Three vinyl-PE-Macromonomers were prepared using Catalyst 5 andActivator B. Catalyst solutions were prepared in a nitrogen purgedVacuum Atmospheres dry box by adding nearly equimolar (1.00:1.05)quantities of the iron complex and activator to 4 mL dry toluene in a 10mL glass vial. The mixture was stirred for 5 min. and then transferredto a clean, oven dried catalyst tube. The basic polymerization procedurefor synthesis of vinyl PE_(mac)-1 is as follows: 2 mL 25 wt % Trin-octylaluminum-in-hexanes scavenger and 400 mL hexanes were added to a2 L stainless steel autoclave reactor. The reactor was heated to 100° C.During this time the catalyst tube was attached to the reactor. Once thereactor temperature equilibrated at 100° C., the catalyst solution wasflushed from the catalyst tube into the reactor with 300 mL hexanes.Following this addition, the reactor was pressurized with 200 psigethylene. In this example, polymerization was carried out for 12minutes, after which time the reactor was cooled and depressurized. Oncethe reactor was depressurized, yet maintained under positive pressurevia a gentle dry nitrogen flush, this polyethylene macromonomer productwas cannulated into septum sealed vials using a slight nitrogen gasoverpressure. The charged vials were transferred into the purged VacuumAtmospheres dry box. PEmac-2 and PEmac-3 were produced following thesame polymerization process, unless noted otherwise. Table A listspolymerization conditions used for preparing the macromonomers.

TABLE A Syntheses of Vinyl-PE Macromonomers with Catalyst 5/Activator BSample Time, min. Temp, (° C.) Yield, g Productivity, g/mmol/hrPE_(mac)-1 12 100 25 155 PE_(mac)-2 30 80 45 1395 PE_(mac)-3 60 60 1003100

The properties of these three macromonomers are listed in Table B.

TABLE B Properties of Vinyl-PE Macromonomers ¹H NMR DSC % GPC-DRI, PEStd Tm, ° C. PE_(mac) M_(N) vinyl M_(N) M_(W) M_(Z) (ΔH, J/g) PE_(mac)-1536 93 240  434    751 76.6, (184) PE_(mac)-2 1129 93 1019  4100  87,175 77.9, (128.8) PE_(mac)-3 688 94 489 3793 235,395 120.5, (199.5) (862)^(a)  (3793)^(a)  (241,617)^(a) ^(a)Light scattering values fromGPC-3D; g′ = 1.00 (versus PE std), data in this table from second melt.

Example 2

Polymerizations with PE_(mac)'s were done inside a purged VacuumAtmospheres dry box. The basic polymerization procedure follows: 2.0 g.of PE_(mac) was placed into an oven dried 10 mL glass vial along with aTeflon coated stir bar. The vial was then heated to 85° C. (above themelting point of this PE_(mac)) on a hot plate. Once the PE_(mac) wasmolten, catalyst and activator were added. In several examples nofurther solvent was added. The contents of the vial are stirred for 1hour on the hot plate and then cooled to ambient temperature. A summaryof polymerizations carried out using the three PE_(mac)'s is provided inTable C.

TABLE C Summary of PE_(brush) Syntheses Using PE_(mac) Cat/ Exam-Activator T_(p). Time Con- ple PE_(mac) Catalyst Act (mg)^(a) (C.) (min)dition 1 1 1 A 2/3 85 60 Neat 2 1 4/MAO A 2/0.2/1.6 85 120 Neat 3 4MAO A2/1/2 110 60 Toluene 4 3 repeat 4/MAO A 20/0.2/16.1 120 30 Neat 5 3 2 A2/3.4 165 60 Neat 6 3 1 A 2/3.0 195 60 Neat 7 3 1 A 2/3.0 195 30 Neat 83 3 B 2/1 195 60 Toluene 9 3 3 B 2/1 115 60 Neat ^(a)Value in italics isvolume of MAO in mL added in addition to Activator A.

TABLE D ¹H NMR Unsaturation Analysis PE_(mac)-1 Example 2t OlefinicGroups per 1000 Carbons* Vinyl 30.8 Not Detected Vinylene  0.9 1.0Vinylidene Not Detected Not Detected Trisubstituted Not Detected NotDetected

A summary is provided in Table E of the ¹H NMR results recorded for theeight polymerizations with PE_(mac)'s. The percentage of totalunsaturations that are vinyls has decreased from the ˜95% range tobetween 0 (not detected) and 25%. Accounting for the impacts of residualvinyls as well as unreacted vinylenes, we can calculate number averagemolecular weights for the brush structures, and these are also tabulatedbelow.

TABLE E Summary ¹H NMR Results for Polymacromonomers (PE_(brush))(Unsat/1000 C.) M_(N) Example vinylenes olefins vinyls vinylidenes %vinyls DP* ¹H NMR* 1 0.91 0.20 0.04 0.36 2.7 340 9,524 2 1.03 0.07 0.000.00 0.00 456 12,727 3 0.60 0.17 0.26 0.01 25 641 17,949 53 1.48 1.150.03 0.09 1 184 5147 6 1.32 0.57 0.47 0.62 16 199 5577 7 1.49 0.65 0.640.80 18 170 4762 9 0.63 0.25 0.09 0.45 6 376 10526 8 1.48 1.15 0.03 0.091 184 5147 *Degree of Polymerization corrected for residual vinyl andvinylene contributions from unconsumed PE_(mac)

The ¹³C NMR spectrum recorded for Example 1 is shown, along with majorpeak assignments, in FIG. 1. The peak resonance positions andassignments for Example 1 are organized in Table F. These assignmentsand intensities, within reasonable limitations, are consistent with thematerial being a product that has a branch on alternating carbons.Assignment nomenclature is described in FIG. 3.

TABLE F ppm* Carbon Type** Assignment Integral Area*** 41.04 CH2 αα 6535.57 CH2 αδ⁺ 60 33.20 CH Branch Point 60 32.22 CH2 3S 73 30.72 CH2 γδ⁺1620 29.98 CH2 δ⁺δ⁺ 29.59 CH2 4S 26.99 CH2 βδ⁺ 58 22.91 CH2 2S 81 14.24CH3 1S 82 ¹³C NMR Spectral Assignments for Example 2 *Shifts relative tobackbone methylene signal set to 29.98 ppm in tetrachloroethane-d2 at120 C. **From DEPT experiment ***Intensity from gated decouplingexperiment (suppressed NOE)Assignment Nomenclature:

Methylene carbons are identified by a pair of Greek letters or a numberpreceeding a S. The Greek symbols are used to indicate the number ofcarbons a methylene is from a methine in either direction. A + sign isused when the closest methine is 4 more carbons away from the methyleneof interest. The ‘S’ terminology identifies carbons at or near the endof saturated n-alkyl chains. The number specifies how many carbons amethylene is from the terminal —CH₃ with the 1S carbon defined as theterminal carbon. FIG. 3 illustrates this particular naming convention.

TABLE G GPC-3D Results for (PE_(mac))_(x) Brushes Made with PE_(mac)'s 1and 3 Ex- ¹H am- NMR brush Mol Wt Moments, DRI (Viscometry) ple M_(N)^(a) % vinyl M_(N) M_(W) M_(Z) g′_(vis) 1 9,524 ~5 2,766 18,771 35,6490.131 (29,525)  (55,732) (101,875)  2 12,727 ~0 4,802 56,259 139,819 0.122 (84,641)  (207,202)  (462,453)  11 40 1,371 12,624 24,466 — 317,949 25 6,715 41,019 86,999 0.187 (52,631)  (111,907)  (198,094)  1050 3,325 18,227 80,842 — 5 5,147 1 3,177  8,356 35,673 0.50  (4420)(10,600) (46,288) 6 5,577 16 3,660 13,038 838,876  0.49 (6,149) (13,689)(103,392)  7 4,762 18 2,896  9,183 135,219  0.494 (6,691) (11,491) (63784) 9 10,526 6 1,595 10,640 28,794 0.370 (7,937) (13,762) (26,460)

In Table G, (g′) vis is defined asg′=[η_(polymacromonomer)/η_(linear HDPE)] (1). Values span the rangefrom 0.122 to 0.50. These values reflect the relative chain mass perunit volume. Due to their topology, the brushes are much more compactthan polyethylene, and the smallest value of g′_(vis) is comparable tothose measured for poly(decene-1) and poly(dodecene-1).

Further Macromonomers were synthesized in a continuous polymerizationsin a 0.5 liter stainless steel continuous autoclave reactor equippedwith a stirrer, steam heating/water cooling element and a pressurecontroller. Solvent, macromonomer and comonomer (if any) are typicallyfirst chilled to −15° C. prior to entering a manifold, and then pumpedinto the reactor. The preactivated catalyst solution((CpMe₅)((1,3-dimethyl Ind)Hf Me₂ and N,N-dimethylanilinium tetra(perfluorophenyl)borate, where Cp=cyclopentadienyl, Me=methyl,Ind=indenyl) is fed into the reactor from a dry box through meteringpumps in a separate line. Solvent (such as hexanes) are pumped into thereactor at a desired rate to control the residence time. The reactor wasfirst fed with solvent, and heated to the desired temperature andcontrolled at a set pressure. The monomers and catalyst were then pumpedinto the reactor. Catalyst feed rate was constant at 2.23×10⁻⁷ mol/minfor all runs. The speed of the stirrer was high enough so the reactorwas operated under continuous stirred tank reactor conditions. Polymersamples were collected for 20 minutes each in a collection box when thesystem reached steady state. Products were dried in a vacuum oven.Reactions were carried out at a pressure of 350 psig and in thetemperature range of 70 to 90° C. A summary of the polymerizations andcharacterization data are provided in Tables H to L.

TABLE H E-co-P Macromonomer Synthesis Conditions Reaction PropyleneEthylene Productivity Con- Example temp feed rate feed rate (g poly/version Number (° C.) (g/min) (SLPM) g catalyst) (%) H-1 60 5.09 3 177357.9 H-2 60 5.09 6 3887 93.8 H-3 60 5.09 9 4971 93.3 H-4 80 5.09 3 163955.4 H-5 80 5.09 6 2890 69.7 H-6 80 5.09 9 4802 90.1

TABLE I Summary of Unsaturations in E-co-P Macromonomers Measured by ¹HNMR Unsat/1000 C. Sam- vi- % ple vinylenes olefins nyls vinylidenesvinyls DP^(a) MN^(a) H-1 0.06 0.13 16.36 0.35 96.8 19.7 828 H-4 0.28 0.719.88 0.54 92.9 15.6 654 ^(a)Calculated assuming one unsaturation perchain

TABLE J Ethylene Content in E-P Macromonomer Products by ¹H NMR ¹H NMRSample Mol fraction C₂ ⁼ Wt Fraction C₂ ⁼ H-1 0.72 0.63 H-4 0.73 0.64

TABLE K Molecular Weight Moments from GPC-DRI (LS) E-P Macromers Wt % C₂^(=a) MN MW MZ MWD g′_(vis) H-1 63 465 1229 5069 2.65 0.678 H-4 64 3741035 4227 2.77 0.516 ^(a)calculated from ¹H NMR, g′vis relative to HDPEstandard.

TABLE L Differential Scanning Calorimetry Data Sample Wt % C₂ ⁼Crystallinity, melting endotherm H-1 63 Broad, sub-ambient peak H-2 74Weak peak 110 C., broad peak ~50 C. H-3 80 Weak peaks 110, 120 C.; broadpeak ~68 C. H-4 64 Broad, weak peak around 25 C. H-5 78 Weak peak 112C.; Broad peak ~58 C. H-6 83 Weak peak ~111 C.; broad peak ~68 C.E-co-P Macromonomer Polymerization Reactions

Macromonomer was added to a solution of catalyst and activator intoluene (1,1′ diphenylmethylene(cyclopentadienyl)(fluorenyl)hafniumdimethyl and N,N-dimethylanilinium tetra (perfluorophenyl)borate) Allcatalysts dissolved in toluene and simply added to the macromonomer atthe designated polymerization temperature.

TABLE M Polymerization with Macromers form Table H E-co-P CatalystMacromonomer Temperature, Macromer prep μM wt, g mM vinyls C. Time, minH-4 3.32 2.18 g 3.32 85 100 H-4 3.32 3.28 g 5.01 85 100 H-4 3.32 4.36 g6.67 85 100

TABLE N E-co-P Polymacromonomer Polymerization Wt % C₂ ⁼ GPC GPC NB# ¹HNMR Mn Mw Mz g′(vis) H-4 64 70101 132006 216733 0.125 H-4 64 43164 83147136449 0.132 H-4 64 85470 157365 253983 0.125 g′vis relative to linearstandard EP copolymer having 64 wt % ethylene.

All documents described herein are incorporated by reference herein,including any priority documents and/or testing procedures to the extentthey are not inconsistent with this text. As is apparent from theforegoing general description and the specific embodiments, while formsof the invention have been illustrated and described, variousmodifications can be made without departing from the spirit and scope ofthe invention. Accordingly, it is not intended that the invention belimited thereby. Likewise, the term “comprising” is consideredsynonymous with the term “including” for purposes of Australian law.

What is claimed is:
 1. A process to produce polymacromonomers comprisingcontacting macromonomer and up to 40 wt % of C₂ to C₁₈ comonomer with acatalyst system capable of polymerizing vinyl terminated macromonomer,wherein, prior to polymerization, the macromonomer has: 1) from 20 to600 carbon atoms, 2) an Mn of 280 g/mol or more, 3) an Mw of 400 g/molor more, 4) an Mz of 600 g/mol or more, 5) an Mw/Mn of 1.5 or more, 6)at least 70% vinyl termination (as measured by ¹H NMR) relative to totalunsaturations, 7) a melting point Tm of 60° C. or more or an Hm of 20J/g or less, and 8) less than 20 wt % aromatic containing monomer; underpolymerization conditions of a temperature of 60 to 130° C. and areaction time of 1 to 90 minutes, wherein the molar ratio of allcomonomer present in the reactor to all macromonomer present in thereactor is 3:1 or less and where conversion of macromonomer topolymacromonomer is 70 wt % or more; and obtaining a polymacromonomerhaving: a) a g value of less than 0.6, b) an Mw of greater than 30,000g/mol, c) an Mn of greater than 20,000 g/mol, d) a branching index(g′)_(vis) of less than 0.5, and e) a melting point of 50° C. or more oran Hm of 20 J/g or less, f) less that 25% vinyl termination (as measuredby ¹H NMR) relative to total unsaturations, g) at least 70 wt %macromonomer, based upon the weight of the polymacromonomer, and h) from0 to 20 wt % aromatic containing monomer, based upon the weight of thepolymacromonomer, and wherein the macromonomer is produced by ahomogenous process for making propylene co-oligomer, said process havingproductivity of at least 4.5×10³ g/mmol/hr, wherein the processcomprises: contacting, at a temperature of from 35° C. to 150° C.,propylene, 0.1 to 70 mol % ethylene and from 0 to about 5 wt % hydrogenin the presence of a catalyst system comprising an activator and atleast one metallocene compound represented by the formulae:

where Hf is hafnium; each X is, independently, selected from the groupconsisting of hydrocarbyl radicals having from 1 to 20 carbon atoms,hydrides, amides, alkoxides, sulfides, phosphides, halogens, dienes,amines, phosphines, ethers, and combinations thereof, (alternately twoX′s may form a part of a fused ring or a ring system); each Q is,independently carbon or a heteroatom; each R¹ is, independently, a C₁ toC₈ alkyl group, R¹ may the same or different as R²; each R² is,independently, a C₁ to C₈ alkyl group; each R³ is, independently,hydrogen, or a substituted or unsubstituted hydrocarbyl group havingfrom 1 to 8 carbon atoms, provided that at least three R³ groups are nothydrogen; each R⁴ is, independently, hydrogen or a substituted orunsubstituted hydrocarbyl group, a heteroatom or heteroatom containinggroup; R⁵ is hydrogen or a C₁ to C₈ alkyl group; R⁶ is hydrogen or a C₁to C₈ alkyl group; each R⁷ is, independently, hydrogen, or a C₁ to C₈alkyl group, provided that at least seven R⁷ groups are not hydrogen; Tis a bridge; each R^(a), is independently, hydrogen, halogen or a C₁ toC₂₀ hydrocarbyl, and two R^(a) can form a cyclic structure includingaromatic, partially saturated, or saturated cyclic or fused ring system;and further provided that any two adjacent R groups may form a fusedring or multicenter fused ring system where the rings may be aromatic,partially saturated or saturated.
 2. The process of claim 1 wherein thepolymacromonomer comprises at least one macromonomer and from 0 to 20 wt% of a C₂ to C₁₈ comonomer, wherein the macromonomer has less than 10 wt% aromatic containing monomer, based upon the weight of themacromonomer.
 3. The process of claim 1 wherein the polymacromonomercontains 0 wt % aromatic containing monomer.
 4. The process of claim 1wherein the polymacromonomer contains 0 wt % styrenic monomer.
 5. Theprocess of claim 1 wherein the macromonomer is isotactic.
 6. The processof claim 1 wherein the polymacromonomer comprises at least 70 wt %macromonomer comprising at least 50 wt % propylene.
 7. The process ofclaim 1 wherein the polymacromonomer comprises at least 70 wt %macromonomer comprising at least 50 wt % ethylene.
 8. The process ofclaim 1 wherein the polymacromonomer comprises two or more differentmacromonomers.
 9. The process of claim 8 wherein the macromonomersdiffer in molecular weight (Mw) by at least 200 g/mol.
 10. The processof claim 8 wherein the first macromonomer has a melting point of 60° C.or more and the second macromonomer has an Hm of 20 J/g or less.
 11. Theprocess of claim 1 wherein the macromonomer comprises a propylenepolymer having a g′_(vis) of 0.95 or less.
 12. The process of claim 1wherein the macromonomer comprises a copolymer of 65 to 80 wt % ethyleneand 20 to 35 wt % propylene (based upon the weight of the copolymer) andhas a Hm of 15 J/g or less.
 13. The process of claim 1 wherein thepolymacromonomer comprises at least one macromonomer and from 0 to 20 wt% of a C₂ to C₁₈ comonomer, wherein, prior to polymerization themacromonomer comprises one or more of: i) propylene co-oligomer havingan Mn of 300 to 30,000 g/mol comprising 10 to 90 mol % propylene and 10to 90 mol % of ethylene, wherein the oligomer has at least X % allylchain ends (relative to total unsaturations), where: 1) X=(−0.94 (mol %ethylene incorporated)+100), when 10 to 60 mol % ethylene is present inthe co-oligomer, and 2) X=45, when greater than 60 and less than 70 mol% ethylene is present in the co-oligomer, and 3) X=(1.83* (mol %ethylene incorporated) −83), when 70 to 90 mol % ethylene is present inthe co-oligomer; and/or ii) propylene oligomer, comprising more than 90mol % propylene and less than 10 mol % ethylene, wherein the oligomerhas: at least 93% allyl chain ends, an Mn of about 500 to about 20,000g/mol, an isobutyl chain end to allylic vinyl group ratio of 0.8:1 to1.35:1.0, and less than 1400 ppm aluminum; and/or iii) propyleneoligomer, comprising at least 50 mol % propylene and from 10 to 50 mol %ethylene, wherein the oligomer has: at least 90% allyl chain ends, Mn ofabout 150 to about 10,000 g/mol, and an isobutyl chain end to allylicvinyl group ratio of 0.8:1 to 1.3:1.0, wherein monomers having four ormore carbon atoms are present at from 0 to 3 mol %; and/or iv) propyleneoligomer, comprising at least 50 mol % propylene, from 0.1 to 45 mol %ethylene, and from 0.1 to 5 mol % C₄ to C₁₂ olefin, wherein the oligomerhas: at least 87% allyl chain ends (alternately at least 90%), an Mn ofabout 150 to about 10,000 g/mol, and an isobutyl chain end to allylicvinyl group ratio of 0.8:1 to 1.35:1.0; and/or v) propylene oligomer,comprising at least 50 mol % propylene, from 0.1 to 45 wt % ethylene,and from 0.1 to 5 mol % diene, wherein the oligomer has: at least 90 %allyl chain ends, an Mn of about 150 to about 10,000 g/mol, and anisobutyl chain end to allylic vinyl group ratio of 0.7:1 to 1.35:1.0.14. The process of claim 13 wherein prior to polymerization, themacromonomer is a propylene co-oligomer having an Mn of 300 to 30,000g/mol comprising 10 to 90 mol % propylene and 10 to 90 mol % ofethylene, wherein the oligomer has at least X % allyl chain ends(relative to total unsaturations), where: 1) X=(−0.94 (mol % ethyleneincorporated)+100), when 10 to 60 mol % ethylene is present in theco-oligomer, and 2) X=45, when greater than 60 and less than 70 mol %ethylene is present in the co-oligomer, and 3) X=(1.83* (mol % ethyleneincorporated) −83), when 70 to 90 mol % ethylene is present in theco-oligomer.
 15. The process claim 13 wherein the macromonomer(s) areliquid at 25° C.
 16. The process of claim 1 wherein the degree ofpolymerization of the polymacromonomer is 6 or more.
 17. The process ofclaim 1 wherein the degree of polymerization of the polymacromonomer is100 or more.
 18. The process of claim 1 wherein the catalyst systemcapable of polymerizing vinyl terminated macromonomer comprises thecompound represented by the formula:


19. The process of claim 1 wherein the catalyst system capable ofpolymerizing vinyl terminated macromonomer comprise one or more of:dimethylsilyl(cyclopentadienyl)(cyclododecylamido)titanium dimethyl,dibenzylmethyl(cyclopentadienyl)(fluorenyl)hafnium dimethyl,diphenylmethyl(cyclopentadienyl)(fluorenyl)hafnium dimethyl,dimethylgermanium bisindenyl hafnium dimethyl,rac-dimethylsilyl(2-methyl-4-phenylindenyl)zirconium dichloride,rac-dimethylsilyl(2-methyl-4-phenylindenyl)zirconium dimethyl,rac-dimethylsilyl(2-methyl-4-phenylindenyl)hafnium dichloride,rac-dimethylsilyl(2-methyl-4-phenylindenyl)hafnium dimethyl,rac-dimethylsilanediylbis(2-methylindenyl)metal dichloride;rac-dimethylsilanediylbis(indenyl)metal dichloride;rac-dimethylsilanediylbis(indenyl)metal dimethyl;rac-dimethylsilanediylbis(tetrahydroindenyl)metal dichloride;rac-dimethylsilanediylbis(tetrahydroindenyl)metal dimethyl;rac-dimethylsilanediylbis(indenyl)metal diethyl; andrac-dibenzylsilanediylbis(indenyl)metal dimethyl; wherein the metal ischosen from Zr, Hf, or Ti.
 20. The process of claim 1 wherein thecatalyst system capable of polymerizing vinyl terminated macromonomercomprises one or more of: N,N-dimethylaniliniumtetrakis(perfluorophenyl)borate, triphenylcarbeniumperfluorotetraphenylborate, dimethylaniliniumperfluorotetranaphthylborate, 4-tert-butylaniliniumbis(pentafluorophenyl)bis(perfluoro-2-naphthyl)borate,4-tert-butylanilinium(pentafluorophenyl)tris(perfluoro-2-naphthyl)borate, dimethylaniliniumtetrakis(perfluor-2-naphthyl)borate, dimethylaniliniumtetrakis(3,5(pentafluorophenyl)perfluorophenylborate); ortris-perfluorophenyl boron.
 21. The process of claim 1 furthercomprising preparing the macromonomer by contacting monomer with acatalyst system comprising activator and catalyst represented by theformula:

or rac-Me₂Si-bis(2-R-indenyl)MX₂ or rac-Me₂Si-bis(2-R,4-Ph-indenyl)MX₂,where R is an alkyl group, Ph is phenyl or substituted phenyl, M is Hf,Zr or Ti, and X is a halogen or alkyl group.
 22. The process of claim 1wherein polymacromonomer comprises 100 wt % propylene or at least 50%propylene with the balance being made up of one or more of ethylene andor C₄ to C₁₂ olefin monomers.
 23. The process of claim 1 wherein thepolymacromonomer comprises at least 80 wt % ethylene with the balancebeing made up of one or more C₃ to C₁₂ olefin monomers.
 24. The processof claim 1 wherein the degree of polymerization of the polymacromonomeris 3 or more.
 25. The process of claim 1 wherein the degree ofpolymerization of the polymacromonomer is 5 or more.
 26. The process ofclaim 1 wherein the macromonomer has an Mw of from 400 to 50,000 g/mol.27. The process of claim 1 wherein the macromonomer has an Mw of from450 to 20,000 g/mol.
 28. The process of claim 1 wherein the macromonomerhas an Mn of from 300 to 12,000 g/mol.
 29. The process of claim 1wherein the macromonomer has an Mn of from 300 to 12,000 g/mol and thepolymacromonomer has an Mn of from 30,000 to 200,000 g/mol.
 30. Theprocess of claim 1 wherein the macromonomer has a Hm of 15 J/g or less.31. The process of claim 1 wherein the degree of polymerization of thepolymacromonomer is 3 or more and the macromonomer has an Mw of 450 to50,000 g/mol.
 32. The process of claim 1 wherein the macromonomerconsists essentially of ethylene.
 33. The process of claim 1 wherein themacromonomer is a propylene co-oligomer having an Mn of 300 to 30,000g/mol comprising 10 to 90 mol % propylene and 10 to 90 mol % ofethylene, wherein the oligomer has at least X % allyl chain ends(relative to total unsaturations), where: 1) X=(−0.94(mol % ethyleneincorporated)+100), when 10 to 60 mol % ethylene is present in theco-oligomer, and 2) X=45, when greater than 60 and less than 70 mol %ethylene is present in the co-oligomer, and 3) X=(1.83* (mol % ethyleneincorporated) −83), when 70 to 90 mol % ethylene is present in theco-oligomer; and has an isobutyl chain end to allylic vinyl group ratioof 0.8:1 to 1.35:1.0.
 34. The process of claim 1 wherein themacromonomer has an isobutyl chain end to allylic vinyl group ratio of0.9:1 to 1.20:1.0.
 35. The process of claim 1 wherein the macromonomeris polymerized with alpha-omega diene.
 36. The process of claim 1wherein the macromonomer comprises less than 1000 ppm aluminum.
 37. Aprocess to produce polymacromonomers comprising contacting macromonomerand up to 40 wt % of C₂ to C₁₈ comonomer with a catalyst system capableof polymerizing vinyl terminated macromonomer, wherein, prior topolymerization, the macromonomer has: 1) from 20 to 600 carbon atoms, 2)an Mn of 280 g/mol or more, 3) an Mw of 400 g/mol or more, 4) an Mz of600 g/mol or more, 5) an Mw/Mn of 1.5 or more, 6) at least 70% vinyltermination (as measured by ¹H NMR) relative to total unsaturations, 7)a melting point Tm of 60° C. or more or an Hm of 20 J/g or less, and 8)0 wt % aromatic containing monomer; under polymerization conditions of atemperature of 60 to 130° C. and a reaction time of 1 to 90 minutes,wherein the molar ratio of all comonomer present in the reactor to allmacromonomer present in the reactor is 3:1 or less and where conversionof macromonomer to polymacromonomer is 70 wt % or more; and obtaining apolymacromonomer having: a) a g value of less than 0.6, b) an Mw ofgreater than 30,000 g/mol, c) an Mn of greater than 20,000 g/mol, d) abranching index (g′)_(vis) of less than 0.5, and e) a melting point of50° C. or more or an Hm of 20 J/g or less, f) less that 25% vinyltermination (as measured by ¹H NMR) relative to total unsaturations, g)at least 70 wt % macromonomer, based upon the weight of thepolymacromonomer, and h) from 0 to 20 wt % aromatic containing monomer,based upon the weight of the polymacromonomer; and wherein themacromonomer is produced by a homogenous process for making propylenehomo-oligomer, said process having a productivity of at least 4.5×10⁶g/mol/min, wherein the process comprises: contacting, at a temperatureof from 30° C. to 120° C., propylene, 0 mol % comonomer and from 0 toabout 5 wt % hydrogen in the presence of a catalyst system comprising anactivator and at least one metallocene compound represented by theformulae:

where Hf is hafnium; each X is, independently, selected from the groupconsisting of hydrocarbyl radicals having from 1 to 20 carbon atoms,hydrides, amides, alkoxides, sulfides, phosphides, halogens, dienes,amines, phosphines, ethers, and combinations thereof, (alternately twoX's may form a part of a fused ring or a ring system); each Q is,independently carbon or a heteroatom; each R¹ is, independently, a C₁ toC₈ alkyl group, R¹ may the same or different as R²; each R² is,independently, a C₁ to C₈ alkyl group; each R³ is, independently,hydrogen, or a substituted or unsubstituted hydrocarbyl group havingfrom 1 to 8 carbon atoms, provided that: 1) all five R³ groups aremethyl, or 2) four R³ groups are not hydrogen and at least one R³ groupis a C₂ to C₈ substituted or unsubstituted hydrocarbyl; each R⁴ is,independently, hydrogen or a substituted or unsubstituted hydrocarbylgroup, a heteroatom or heteroatom containing group; R⁵ is hydrogen or aC₁ to C₈ alkyl group; R⁶ is hydrogen or a C₁ to C₈ alkyl group; each R⁷is, independently, hydrogen, or a C₁ to C₈ alkyl group, provided that atleast seven R⁷ groups are not hydrogen; T is a bridge; each R^(a), isindependently, hydrogen, halogen or a C₁ to C₂₀ hydrocarbyl, and twoR^(a) can form a cyclic structure; and further provided that any twoadjacent R groups may form a fused ring or multicenter fused ring systemwhere the rings may be aromatic, partially saturated or saturated. 38.The process of claim 37 wherein the degree of polymerization of thepolymacromonomer is 6 or more.
 39. The process of claim 37 wherein thedegree of polymerization of the polymacromonomer is 100 or more.
 40. Theprocess of claim 37 wherein the catalyst system capable of polymerizingvinyl terminated macromonomer comprises the compound represented by theformula:


41. The process of claim 37 wherein the catalyst system capable ofpolymerizing vinyl terminated macromonomer comprise one or more of:dimethylsilyl(cyclopentadienyl)(cyclododecylamido)titanium dimethyl,dibenzylmethyl(cyclopentadienyl)(fluorenyl)hafnium dimethyl,diphenylmethyl(cyclopentadienyl)(fluorenyl)hafnium dimethyl,dimethylgermanium bisindenyl hafnium dimethyl,rac-dimethylsilyl(2-methyl-4-phenylindenyl)zirconium dichloride,rac-dimethylsilyl(2-methyl-4-phenylindenyl)zirconium dimethyl,rac-dimethylsilyl(2-methyl-4-phenylindenyl)hafnium dichloride,rac-dimethylsilyl(2-methyl-4-phenylindenyl) hafnium dimethyl,rac-dimethylsilanediylbis(2-methylindenyl)metal dichloride;rac-dimethylsilanediylbis(indenyl)metal dichloride;rac-dimethylsilanediylbis(indenyl)metal dimethyl;rac-dimethylsilanediylbis(tetrahydroindenyl)metal dichloride;rac-dimethylsilanediylbis(tetrahydroindenyl)metal dimethyl;rac-dimethylsilanediylbis(indenyl)metal diethyl; andrac-dibenzylsilanediylbis(indenyl)metal dimethyl; wherein the metal ischosen from Zr, Hf, or Ti.
 42. The process of claim 37 wherein thecatalyst system capable of polymerizing vinyl terminated macromonomercomprises one or more of: dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetra(perfluorophenyl)borate,triphenylcarbonium perfluorotetraphenylborate, dimethylaniliniumperfluorotetranaphthylborate, 4-tert-butylaniliniumbis(pentafluorophenyl)bis(perfluoro-2-naphthyl)borate,4-tert-butylanilinium(pentafluorophenyl)tris(perfluoro-2-naphthyl)borate, dimethylaniliniumtetrakis(perfluoro-2-naphthyl)borate, dimethylaniliniumtetrakis(3,5(pentafluorophenyl)perfluorophenylborate); ortris-perfluorophenyl boron.
 43. The process of claim 37 furthercomprising preparing the macromonomer by contacting monomer with acatalyst system comprising activator and catalyst represented by theformula:

or rac-Me₂Si-bis(2-R-indenyl)MX₂ or rac-Me₂Si-bis(2-R,4-Ph-indenyl)MX₂,where R is an alkyl group, Ph is phenyl or substituted phenyl, M is Hf,Zr or Ti, and X is a halogen or alkyl group.
 44. The process of claim 37wherein the polymacromonomer comprises at least one macromonomer andfrom 0 to 20 wt % of a C₂ to C₁₈ comonomer, based upon the weight of themacromonomer.
 45. The process of claim 37 wherein the degree ofpolymerization of the polymacromonomer is 3 or more.
 46. The process ofclaim 37 wherein the degree of polymerization of the polymacromonomer is5 or more.
 47. The process of claim 37 wherein the macromonomer isisotactic.
 48. The process of claim 37 wherein the polymacromonomercomprises at least 70 wt % macromonomer comprising at least 50 wt %propylene.
 49. The process of claim 37 wherein the polymacromonomercomprises two or more different macromonomers.
 50. The process of claim49 wherein the macromonomers differ in molecular weight (Mw) by at least200 g/mol.
 51. The process of claim 49 wherein the first macromonomerhas a melting point of 60° C. or more and the second macromonomer has anHm of 20 J/g or less.
 52. The process of claim 37 wherein themacromonomer comprises a propylene polymer having a g′_(vis) of 0.95 orless.
 53. The process of claim 37 wherein the polymacromonomer comprisesat least one macromonomer and from 0 to 20 wt % of a C₂ to C₁₈comonomer, wherein, prior to polymerization, the macromonomer comprisesone or more homooligomer(s), comprising propylene, wherein the oligomerhas: at least 93% allyl chain ends, an Mn of about 500 to about 20,000g/mol, an isobutyl chain end to allylic vinyl group ratio of 0.8:1 to1.2:1.0, and less than 1400 ppm aluminum.
 54. The process of claim 37wherein the macromonomer(s) are liquid at 25° C.
 55. The process ofclaim 37 wherein polymacromonomer comprises 100 wt % propylene or atleast 50% propylene with the balance being made up of one or more ofethylene and or C₄ to C₁₂ olefin monomers.
 56. The process of claim 37wherein the macromonomer has an Mw of from 450 to 15,000 g/mol.
 57. Theprocess of claim 37 wherein the macromonomer has an Mn of from 300 to15,000 g/mol.
 58. The process of claim 37 wherein the macromonomer has aHm of 15 J/g or less and the polymacromonomer has an Mw of 40,000 to700,000 g/mol.
 59. The process of claim 37 wherein the degree ofpolymerization of the polymacromonomer is 3 or more and the macromonomerhas an Mw of 450 to 50,000 g/mol.
 60. The process of claim 37 whereinthe macromonomer has an isobutyl chain end to allylic vinyl group ratioof 0.9:1 to 1.1:1.0.
 61. The process of claim 37 wherein themacromonomer comprises a homooligomer, comprising propylene, wherein theoligomer has: at least 93% allyl chain ends, an Mn of about 500 to about20,000 g/mol, an isobutyl chain end to allylic vinyl group ratio of0.8:1 to 1.2:1.0, and less than 1400 ppm aluminum.